Graft polymers and use thereof in cosmetic formulations

ABSTRACT

The invention relates to graft polymers obtainable by free-radical graft polymerization of a) at least one N-vinyl-containing monomer b) optionally one or more further copolymerizable monomers onto a polymeric graft base c), which comprises at least one compound from the group c1) and at least one compound from the group c2), where c1) represents polyether-containing compounds c2) represents polymers which comprise at least 5% by weight of vinylpyrrolidone units d) optionally at least one crosslinker. and to their use in cosmetic preparations.

The invention relates to graft polymers and to their use as aconstituent in cosmetic compositions. The graft polymers are produced bygrafting monoethylenically unsaturated, open-chain N-vinylamideunit-comprising monomers onto a polymeric graft base which consists ofat least 2 compounds.

Polymers are used widely in cosmetics and medicine. In soaps, creams andlotions, for example, they usually serve as formulation agents, e.g. asthickeners, foam stabilizers or water absorbents, or else foralleviating the irritative action of other ingredients, or for improvingthe dermal application of active ingredients. By contrast, their task inhair cosmetics is to influence the properties of the hair.

For example, conditioners are used for improving the dry and wetcombability, feel, shine and appearance, and for imparting antistaticproperties to the hair. Preference is given to using water-solublepolymers with polar, frequently cationic functionalities which have agreater affinity to the surface of the hair, which is negative as aresult of its structure. The structure and mode of action of varioushair-treatment polymers are described in Cosmetic & Toiletries 103(1988) 23. Commercially available conditioning polymers are, forexample, cationic hydroxyethylcellulose, cationic polymers based onN-vinylpyrrolidone, e.g. copolymers of N-vinylpyrrolidone andquaternized N-vinylimidazole, acrylamide and diallyldimethylammoniumchloride or silicones.

For setting hairstyles, use is made of vinyllactam homopolymers andcopolymers and polymers containing carboxylate groups. Requirements forhair-setting resins are, for example, a strong hold at high atmospherichumidity, elasticity, wash-off from the hair, compatibility in theformulation and a pleasant feel of the hair.

The combination of different properties, such as, for example, stronghold and pleasant feel of the hair, often presents difficulties.

WO-A-96/03969 describes haircare compositions comprising anN-vinylformamide homopolymer or a copolymer of N-vinylformamide unitsand a further vinyl monomer chosen from styrenes, alkyl esters ofacrylic and methacrylic acid, vinyl esters of the formulaCH₂═CH—OCO-alkyl, N-alkyl-substituted acrylamides and methacrylamides,esters of fumaric, itaconic and maleic acid, vinyl ethers,hydroxy-functionalized acrylates and methacrylates, acrylamide,non-alkyl-substituted acrylamides and cyclic amides. A specific exampleof a cyclic amide is N-vinylpyrrolidone. Further examples of vinylmonomers are secondary, tertiary and quaternary amines, such asdimethyldiallylammonium chloride, dimethylaminoethyl methacrylate ordimethylaminopropyl methacrylate.

DE 19640363 describes copolymers of N-vinylformamide and quaternizedN-vinylimidazole and the uses thereof in cosmetics.

DE 19907587.5 describes the use of polymers obtainable by free-radicalpolymerization of at least one vinyl ester in the presence ofpolyether-containing compounds and optionally one or morecopolymerizable monomers, and subsequent at least partial hydrolysis ofthe ester function in hair cosmetic formulations. A copolymerizablemonomer is, inter alia, vinylformamide.

DE-A1-44 09 903 describes graft polymers comprising N-vinyl units,processes for their preparation and their use. Here, monoethylenicallyunsaturated monomers are grafted onto a graft base which is a polymerwhich in each case comprises at least 5% by weight of units of theformulae

where R¹, R²═H or C₁-C₆-alkyl. Suitable monoethylenically unsaturatedmonomers are all ethylenically unsaturated monomers whose polymerizationis not inhibited by the amine groups in free or in salt form, such as,for example, monoethylenically unsaturated mono- and dicarboxylic acids,their salts and esters with C₁-C₃₀-alcohols. Suitability of these graftcopolymers as active ingredient in cosmetic formulations is notmentioned.

WO 96/34903 describes graft polymers comprising N-vinyl units, processesfor their preparation and their use. Here, monoethylenically unsaturatedmonomers are grafted onto a graft base which is a polymer whichcomprises at least 3 units of a C₂-C₄-alkylene oxide, and/orpolytetrahydrofuran, and then at least partially hydrolyzed. Suitabilityof these graft copolymers as active ingredient in cosmetic formulationsis not mentioned.

U.S. Pat. No. 5,334,287 discloses graft polymers obtainable byfree-radical-initiated polymerization of N-vinylcarboxamides, preferablyN-vinylformamide, and optionally other monomers in the presence ofmonosaccharides, oligosaccharides, polysaccharides or derivativesthereof in each case, and optionally hydrolysis of the copolymerizedN-vinylcarboxamide group to form vinylamine units. Suitability of thesegraft copolymers as active ingredient in cosmetic formulations is notmentioned.

In WO 9825981, amphiphilic graft polymers are synthesized by graftinghydrophobic monomers, such as, for example, styrene, onto polymers whichcomprise structural elements of the formula (IV) and/or (V). The graftpolymers obtained are used inter alia as additives in cosmeticformulations.

DE-A1-196 40 363 claims the use of water-soluble copolymers as activeingredient in cosmetic formulations. As a characteristic structuralelement, the copolymer comprises units of the formula (VI)

in which A is a chemical bond or an alkylene group, the radicals R¹⁷,independently of one another, are H, alkyl, cycloalkyl, aryl or aralkyl,and R¹⁸ is H, alkyl or aralkyl.

Bodycare creams which comprise a monoaldehyde-modified vinylaminepolymer are known from U.S. Pat. No. 5,270,379.

Copolymers which are used, for example, as hair-setting agents and arebuilt up from N-vinylamide monomers of the formula

in which R1 and R2 are H or C₁-C₅-alkyl, and the comonomer is chosenfrom vinyl ethers, vinyllactams, vinyl halides, vinyl esters ofmonobasic saturated carboxylic acids, (meth)acrylic esters, amides andnitriles and esters, anhydrides and imides of maleic acid are known fromDE 14 95 692.

U.S. Pat. No. 4,713,236 describes hair conditioners based on polymerscomprising vinylamine units. Particular mention is made here ofpolyvinylamine and salts thereof, α-substituted polyvinylamines, suchas, for example, poly(a-aminoacrylic acid) and also copolymers which, inaddition to vinylamine, comprise, in copolymerized form, comonomers suchas vinyl alcohol, acrylic acid, acrylamide, maleic anhydride, vinylsulfonate and 2-acrylamido-2-methylpropanesulfonic acid.

WO 02/15854 A1 describes the use of hydrophilic graft copolymers withN-vinylamine and/or open-chain N-vinylamine units in cosmeticformulations. Graft polymers which are formed by grafting onto apolymeric graft base which consists of at least 2 compounds are notdescribed.

It is an object of the present invention to find polymers which arehighly suitable for cosmetic applications and which, for example in thefield of hair cosmetics, have good applications-related properties, suchas pleasant feel, and at the same time a good conditioning action and agood setting action.

Despite extensive efforts, there still remains a need for improvementwith polymers for producing elastic hairstyles with simultaneouslystrong hold, even at high atmospheric humidity, good ability to bewashed off and good feel of the hair. The need for improvement likewiseconsists, in the case of polymers for producing readily combable,detanglable hair and for the conditioning of skin and hair, in theirsensorily perceptible properties, such as feel, volume, manageabilityetc. Also desirable are clear aqueous preparations of these polymerswhich are accordingly characterized by good compatibility with otherformulation constituents.

In addition, there is a need for polymers which are suitable asconditioning agents for cosmetic preparations and which can be preparedwith a high solids content. Of particular interest are polymers whichhave a high solids content, have a low viscosity whilst at the same timeretaining the applications-related properties (such as, for example,combability).

We have found that this object is achieved by graft polymers obtainableby free-radical graft polymerization of

-   -   a) at least one open-chain N-vinylamide compound of the formula        (I)    -    where R¹, R², R³═H or C₁— to C₆-alkyl, and    -   b) optionally one or more further copolymerizable monomers onto        a polymeric graft base c), which comprises at least one compound        from the group c1) and at least one compound from the group c2),        where    -   c1) represents polyether-containing compounds    -   c2) represents polymers which comprise at least 5% by weight of        vinylpyrrolidone units,    -   d) optionally at least one crosslinker.

Depending on the degree of grafting, the polymers used according to theinvention are understood as meaning either pure graft polymers, or elsemixtures of the abovementioned graft polymers with ungrafted compoundsc1) and c2) and homopolymers or copolymers of the monomers a) and b).

In a preferred embodiment, the graft polymers are water-soluble orwater-dispersible.

Water-soluble polymers are understood here as meaning polymers whichdissolve in water at 20° C. in an amount of at least 1 g/l.Water-dispersible polymers are understood here as meaning polymers whichdisintegrate into dispersible particles with stirring.

Monomer a)

N-vinylamides and/or N-vinyllactams, for example, are suitable asN-vinyl-containing monomer a).

Suitable as N-vinyl-containing monomer a) are, for example,N-vinylamides of the formula (I)

where R¹, R², R³═H or C₁— to C₆-alkyl.

For the preparation of the polymers used according to the invention, thefollowing monomers are, for example, used as open-chain N-vinylamidecompound a) of the formula (I): N-vinylformamide,N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide,N-vinyl-N-ethylacetamide, N-vinylpropionamide,N-vinyl-N-methylpropionamide and N-vinylbutyramide.

Further suitable N-vinyl-containing monomers a) are N-vinyllactams ofthe formula (II)

where n=1, 2, 3.

Examples of monomers of the formula (II) are N-vinylpyrrolidone (n=1)and N-vinylcaprolactam (n=3).

Further suitable N-vinyl-containing monomers a) are N-vinylpiperidone,N-vinyloxazolidone and N-vinyltriazole.

In a preferred embodiment of the invention, an N-vinylamide, inparticular N-vinylformamide, is used as monomer a).

It is of course also possible to copolymerize mixtures of the respectivemonomers from the group a) such as, for example, mixtures ofN-vinylformamide and N-vinylacetamide.

For the preparation of the graft polymers according to the invention,the following monomers are, for example, used as open-chain N-vinylamidecompound a) of the formula (I): N-vinylformamide,N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide,N-vinyl-N-ethylacetamide, N-vinylpropionamide,N-vinyl-N-methylpropionamide and N-vinylbutyramide. From this group ofmonomers, preference is given to using N-vinylformamide.

Monomer b)

As well as comprising the monomers a) and the graft base c), the graftpolymers can comprise one or more further monomers b). The preferredadditionally used copolymerizable monomers b) can be described by thefollowing formula:X—C(O)CR²⁰═CHR¹⁹where

X is chosen from the group of radicals —OH, —OM, —OR²¹, NH₂, —NHR²¹,N(R²¹)₂;

M is a cation chosen from the group consisting of: Na⁺, K⁺, Mg⁺⁺, Ca⁺⁺,Zn⁺⁺, NH₄ ⁺, alkylammonium, dialkylammonium, trialkylammonium andtetraalkylammonium;

the radicals R²¹ may be identical or different and are chosen from thegroup consisting of —H, C₁-C₄₀ linear- or branched-chain alkyl radicals,N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl,hydroxypropyl, methoxypropyl or ethoxypropyl.

R²⁰ and R¹⁹ are, independently of one another, chosen from the groupconsisting of: —H, C₁-C₈ linear- or branched-chain alkyl chains,methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl.

Representative but nonlimiting examples of suitable monomers b) are, forexample, acrylic acid or methacrylic acids or salts, esters and amidesthereof. The salts can be derived from any desired nontoxic metal,ammonium or substituted ammonium counterion.

The esters can be derived from C₁-C₄₀ linear, C₃-C₄₀ branched-chain orC₃-C₄₀ carbocyclic alcohols, from polyfunctional alcohols having 2 toabout 8 hydroxyl groups, such as ethylene glycol, hexylene glycol,glycerol and 1,2,6-hexanetriol, from amino alcohols or from alcoholethers, such as methoxyethanol and ethoxyethanol, (alkyl)polyethyleneglycols, (alkyl)polypropylene glycols and ethoxylated fatty alcohols,for example C₁₂-C₂₄-fatty alcohols reacted with 1 to 200 ethylene oxideunits.

Also suitable are N,N-dialkylaminoalkyl acrylates and methacrylates andN-dialkylaminoalkylacrylamides and -methacrylamides of the formula (VII)

where

-   -   R²²═H, alkyl having 1 to 8 carbon atoms,    -   R²³═H, methyl,    -   R²⁴=alkylene having 1 to 24 carbon atoms, optionally substituted        by alkyl,    -   R²⁵, R²⁶═C₁-C₄₀-alkyl radical,    -   Z=nitrogen when g=1 or oxygen when g=0

The amides can be unsubstituted, N-alkyl- orN-alkylamino-monosubstituted or N,N-dialkyl-substituted orN,N-dialkylamino-disubstituted, in which the alkyl or alkylamino groupsare derived from C₁-C₄₀ linear, C₃-C₄₀ branched-chain, or C₃-C₄₀carbocyclic units. Additionally, the alkylamino groups may bequaternized.

Preferred comonomers of the formula VII areN,N-dimethylaminomethyl(meth)acrylate,N,N-diethylaminomethyl(meth)acrylate,N,N-dimethylaminoethyl(meth)acrylate,N,N-diethylaminoethyl(meth)acrylate,N-[3-(dimethylamino)propyl]methacrylamide andN-[3-(dimethylamino)propyl]acrylamide.

Comonomers b) which can likewise be used are substituted acrylic acids,and salts, esters and amides thereof, where the substituents on thecarbon atoms are in the two or three position of the acrylic acid, and,independently of one another, are chosen from the group consisting ofC₁-C₄ alkyl, —CN, COOH, particularly preferably methacrylic acid,ethacrylic acid and 3-cyanoacrylic acid. These salts, esters and amidesof these substituted acrylic acids can be chosen as described above forthe salts, esters and amides of acrylic acid.

Other suitable comonomers b) are allyl esters of C₁-C₄₀ linear, C₃-C₄₀branched-chain or C₃-C₄₀ carbocyclic carboxylic acids, vinyl or allylhalides, preferably vinyl chloride and allyl chloride, vinyl ethers,preferably methyl, ethyl, butyl or dodecyl vinyl ethers, vinyllactams,preferably vinylpyrrolidone and vinylcaprolactam, vinyl- orallyl-substituted heterocyclic compounds, preferably vinylpyridine,vinyloxazoline and allylpyridine.

Also suitable are N-vinylimidazoles of the formula VIII in which R²⁷ toR²⁹, independently of one another, are hydrogen, C₁-C₄-alkyl or phenyl:

Further suitable comonomers b) are diallylamines of the formula (IX)

where R³⁰═C₁— to C₂₄-alkyl.

Further suitable comonomers b) are vinylidene chloride; and hydrocarbonswith at least one carbon-carbon double bond, preferably styrene,alpha-methylstyrene, tert-butylstyrene, butadiene, isoprene,cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutylene,vinyltoluene, and mixtures of these monomers.

Particularly suitable comonomers b) are acrylic acid, methacrylic acid,ethylacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate,n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexylacrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate,propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate,t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate,methyl ethacrylate, ethyl ethacrylate, n-butyl ethacrylate, isobutylethacrylate, t-butyl ethacrylate, 2-ethylhexyl ethacrylate, decylethacrylate, stearyl (meth)acrylate, 2,3-dihydroxypropyl acrylate,2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropylacrylates, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate,2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-methoxyethylethacrylate, 2-ethoxyethyl methacrylate, 2-ethoxyethyl ethacrylate,hydroxypropyl methacrylates, glyceryl monoacrylate, glycerylmonomethacrylate, polyalkylene glycol (meth)acrylates, unsaturatedsulfonic acids, such as, for example, acrylamidopropanesulfonic acid;

acrylamide, methacrylamide, ethacrylamide, N-methylacrylamide,N,N-dimethylacrylamide, N-ethylacrylamide, N-isopropylacrylamide,N-butylacrylamide, N-t-butylacrylamide, N-octylacrylamide,N-t-octylacrylamide, N-octadecylacrylamide, N-phenylacrylamide,N-methylmethacrylamide, N-ethylmethacrylamide, N-dodecylmethacrylamide,1-vinylimidazole, 1-vinyl-2-methylvinylimidazole,N,N-dimethylaminomethyl(meth)acrylate,N,N-diethylaminomethyl(meth)acrylate,N,N-dimethylaminoethyl(meth)acrylate,N,N-diethylaminoethyl(meth)acrylate,N,N-dimethylaminobutyl(meth)acrylate,N,N-diethylaminobutyl(meth)acrylate,N,N-dimethylaminohexyl(meth)acrylate,N,N-dimethylaminooctyl(meth)acrylate,N,N-dimethylaminododecyl(meth)acrylate,N-[3-(dimethylamino)propyl]methacrylamide,N-[3-(dimethylamino)propyl]acrylamide,N-[3-(dimethylamino)butyl]methacrylamide,N-[8-(dimethylamino)octyl]methacrylamide,N-[12-(dimethylamino)dodecyl]-methacrylamide,N-[3-(diethylamino)propyl]methacrylamide,N-[3-(diethylamino)propyl]acrylamide;

maleic acid, fumaric acid, maleic anhydride and its monoesters, crotonicacid, itaconic acid, diallyldimethylammonium chloride, vinyl ethers (forexample: methyl, ethyl, butyl or dodecyl vinyl ethers), methyl vinylketone, maleimide, vinylpyridine, vinylimidazole, vinylfuran, styrene,styrene sulfonate, allyl alcohol, and mixtures thereof.

Of these, particular preference is given to acrylic acid, methacrylicacid, maleic acid, fumaric acid, crotonic acid, maleic anhydride andmonoesters thereof, methyl acrylate, methyl methacrylate, ethylacrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate,t-butyl acrylate, t-butyl methacrylate, isobutyl acrylate, isobutylmethacrylate, 2-ethylhexyl acrylate, stearyl acrylate, stearylmethacrylate, N-t-butylacrylamide, N-octylacrylamide, 2-hydroxyethylacrylate, hydroxypropyl acrylates, 2-hydroxyethyl methacrylate,hydroxypropyl methacrylates, alkylene glycol(meth)acrylates, styrene,unsaturated sulfonic acids, such as, for example,acrylamidopropanesulfonic acid, vinylpyrrolidone, vinylcaprolactam,vinyl ethers (e.g.: methyl, ethyl, butyl or dodecyl vinyl ethers),1-vinylimidazole, 1-vinyl-2-methylimidazole, N,N-dimethylaminomethylmethacrylate and N-[3-(dimethylamino)propyl]methacrylamide;3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazoliummethylsulfate, N,N-dimethylaminoethyl methacrylate,N-[3-(dimethylamino)propyl]methacrylamide quaternized with methylchloride, methyl sulfate or diethyl sulfate.

Monomers containing a basic nitrogen atom can be quaternized here in thefollowing manner:

For the quaternization of the amines, alkyl halides having 1 to 24carbon atoms in the alkyl group are, for example, suitable, e.g. methylchloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide,propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride andbenzyl halides, in particular benzyl chloride and benzyl bromide.Further suitable quaternizing agents are dialkyl sulfates, in particulardimethyl sulfate or diethyl sulfate. The quaternization of the basicamines can also be carried out with alkylene oxides, such as ethyleneoxide or propylene oxide, in the presence of acids. Preferredquaternizing agents are, methyl chloride, dimethyl sulfate or diethylsulfate.

The quaternization can be carried out before the polymerization or afterthe polymerization.

Furthermore, the reaction products of unsaturated acids, such as, forexample acrylic acid or methacrylic acid, with a quaternizedepichlorohydrin of the formula (X)(R³¹═C₁— to C₄₀-alkyl) can be used.

Examples thereof are:

(meth)acryloyloxyhydroxypropyltrimethylammonium chloride and(meth)acryloyloxyhydroxypropyltriethylammonium chloride.

The basic monomers can also be cationized by neutralizing them withmineral acids, such as, for example, sulfuric acid, hydrochloric acid,hydrobromic acid, hydroiodic acid, phosphoric acid or nitric acid, orwith organic acids, such as, for example, formic acid, acetic acid,lactic acid or citric acid.

In addition to the abovementioned monomers, it is also possible to use,as comonomers b), so-called macromonomers, such as, for example,silicone-containing macromonomers with one or more free-radicallypolymerizable groups, or alkyloxazoline macromonomers as are described,for example, in EP 408 311.

In addition, it is also possible to use fluorine-containing monomers, asare described, for example, in EP-A 558 423, or compounds which have acrosslinking action or regulate the molecular weight, in combination oron their own.

The further copolymerizable monomers b) are preferably used in an amountof 0-40% by weight, preferably 0-25% by weight, particularly preferably0-15%.

Regulator e)

In one embodiment of the invention, the graft polymers can be obtainedby carrying out the free-radical polymerization in the presence of atleast one regulator e).

Regulators e) which can be used are the customary compounds known to theperson skilled in the art, such as, for example, sulfur compounds (e.g.:mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid ordodecylmercaptan), and tribromochloromethane or other compounds whichhave a regulating effect on the molecular weight of the resultingpolymers.

Where appropriate, it is also possible to use silicone compounds whichcontain thiol groups. Preference is given to using silicone-freeregulators.

The regulator e) is preferably used in an amount of 0-5% by weight,preferably 0-2.5% by weight, particularly preferably 0-1.5%.

Crosslinker d)

In one preferred embodiment, the graft polymers are prepared in thepresence of a crosslinker d).

Monomers d), which have a crosslinking function, are compounds with atleast 2 ethylenically unsaturated, nonconjugated double bonds in themolecule.

Suitable crosslinkers d) are, for example, acrylic esters, methacrylicesters, allyl ethers or vinyl ethers of at least dihydric alcohols. TheOH groups of the parent alcohols may be completely or partiallyetherified or esterified; however, the crosslinkers comprise at leasttwo ethylenically unsaturated groups.

Examples of the parent alcohols are dihydric alcohols, such as1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol,1,3-butanediol, 2,3-butanediol, 1,4-butanediol, but-2-ene-1,4-diol,1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol,1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, neopentyl glycol,3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexanediol,2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol,1,4-cyclohexanediol, 1,4-bis(hydroxymethyl)cyclohexane,mononeopentylglycol hydroxypivalate, 2,2-bis(4-hydroxyphenyl)propane,2,2-bis[4-(2-hydroxypropyl)phenyl]propane, diethylene glycol,triethylene glycol, tetraethylene glycol, dipropylene glycol,tripropylene glycol, tetrapropylene glycol, 3-thiopentane-1,5-diol, andalso polyethylene glycols, polypropylene glycols andpolytetrahydrofurans with molecular weights of in each case 200 to10000. Apart from the homopolymers of ethylene oxide or propylene oxide,it is also possible to use block copolymers of ethylene oxide orpropylene oxide or copolymers which comprise ethylene oxide andpropylene oxide groups in incorporated form. Examples of parent alcoholswith more than two OH groups are trimethylolpropane, glycerol,pentaerythritol, 1,2,5-pentanetriol, 1,2,6-hexanetriol,triethoxycyanuric acid, sorbitan, sugars, such as sucrose, glucose,mannose. It is of course also possible to use the polyhydric alcoholsalso following reaction with ethylene oxide or propylene oxide in theform of the corresponding ethoxylates or propoxylates, respectively. Thepolyhydric alcohols can also firstly be converted into the correspondingglycidyl ethers by reaction with epichlorohydrin.

Further suitable crosslinkers are the vinyl esters or the esters ofmonohydric, unsaturated alcohols with ethylenically unsaturated C₃— toC₆-carboxylic acids, for example acrylic acid, methacrylic acid,itaconic acid, maleic acid or fumaric acid. Examples of such alcoholsare allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octen-3-ol,9-decen-1-ol, dicyclopentenyl alcohol, 10-undecen-1-ol, cinnamylalcohol, citronellol, crotyl alcohol or cis-9-octadecen-1-ol. It is,however, also possible to esterify the monohydric, unsaturated alcoholswith polyhydric carboxylic acids, for example malonic acid, tartaricacid, trimellitic acid, phthalic acid, terephthalic acid, citric acid orsuccinic acid.

Further suitable crosslinkers are esters of unsaturated carboxylic acidswith the above-described polyhydric alcohols, for example of oleic acid,crotonic acid, cinnamic acid or 10-undecenoic acid.

Further suitable crosslinkers d) are straight-chain or branched, linearor cyclic, aliphatic or aromatic hydrocarbons which have at least twodouble bonds which, in the case of aliphatic hydrocarbons, must not beconjugated, e.g. divinylbenzene, divinyltoluene, 1,7-octadiene, 19-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane orpolybutadienes with molecular weights of from 200 to 20 000.

Further suitable crosslinkers are the acrylamides, methacrylamides andN-allylamines of at least difunctional amines. Such amines are, forexample, diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane,1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, piperazine,diethylenetriamine or isophoronediamine. Likewise suitable are theamides of allylamine and unsaturated carboxylic acids, such as acrylicacid, methacrylic acid, itaconic acid, maleic acid, or at least dibasiccarboxylic acids, as have been described above.

Triallylamine and triallylmonoalkylammonium salts, e.g.triallylmethylammonium chloride or methylsulfate, are also suitable ascrosslinkers.

Also suitable are N-vinyl compounds of urea derivatives, at leastdifunctional amides, cyanurates or urethanes, for example of urea,ethyleneurea, propyleneurea or tartaramide, e.g.N,N′-divinylethyleneurea or N,N′-divinylpropyleneurea.

Further suitable crosslinkers are divinyldioxane, tetraallylsilane ortetravinylsilane.

It is of course also possible to use mixtures of the abovementionedcompounds. Preference is given to using those crosslinkers which aresoluble in the monomer mixture.

Particularly preferably used crosslinkers are, for example,methylenebisacrylamide, triallylamine and triallylalkylammonium salts,divinylimidazole, pentaerythritol triallyl ether,N,N′-divinylethyleneurea, reaction products of polyhydric alcohols withacrylic acid or methacrylic acid, methacrylic esters and acrylic estersof polyalkylene oxides or polyhydric alcohols which have been reactedwith ethylene oxide and/or propylene oxide and/or epichlorohydrin.

Very particularly preferred crosslinkers are pentaerythritol triallylether, methylenebisacrylamide, N,N′-divinylethyleneurea, triallylamineand triallylmonoalkylammonium salts, and acrylic esters of glycol,butanediol, trimethylolpropane or glycerol or acrylic esters of glycol,butanediol, trimethylolpropane or glycerol reacted with ethylene oxideand/or epichlorohydrin.

Polymeric Graft Base c)

The polymeric graft base c) comprises at least one compound chosen fromthe group c1) and at least one compound chosen from the group c2), where

-   -   c1) are polyether-containing compounds    -   c2) are polymers which comprise at least 5% by weight of        vinylpyrrolidone units in copolymerized form.        Graft Base c1)

Polyether-containing compounds c1) which can be used are eitherpolyalkylene oxides based on ethylene oxide, propylene oxide, butyleneoxide and further alkylene oxides, and also polyglycerol. Depending onthe nature of the monomer building blocks, the polymers comprise thefollowing structural units:—(CH₂)₂—O—, —(CH₂)₃—O—, —(CH₂)₄—O—, —CH₂—CH(R⁹)—O—, —CH₂—CHOR¹⁰—CH₂—O—

where R⁹ is C₁-C₂₄-alkyl;

R¹⁰ is hydrogen, C_(1-C) ₂₄-alkyl, R⁹—C(═O)—, R⁹—NH—C(═O)—.

The structural units may either be homopolymers or random copolymers andblock copolymers.

Suitable graft bases c1) are, in particular, water-solublepolyether-containing compounds. In this connection, it is possible touse either polyalkylene oxides based on ethylene oxide, propylene oxide,butylene oxide and further alkylene oxides, as well as polyglycerol. Inthis connection, the structural units may either be homopolymers orrandom copolymers and block copolymers.

As graft base c1), preference is given to using compounds of thefollowing formula (I):

in which the variables, independently of one another, have the followingmeanings:

R¹ is hydrogen, C₁-C₂₄-alkyl, R⁶—C(═O)—, R⁶—NH—C(═O)—, polyalcoholradical;

R⁵ is hydrogen, C₁-C₂₄-alkyl, R⁶—C(═O)—, R⁶—NH—C(═O)—;

R²to R⁴ are —(CH₂)₂—, —(CH₂)₃—, —(CH₂)₄—, —CH₂—CH(R⁶)—, —CH₂—CHOR⁷—CH₂—;

R⁶ is C₁-C₂₄-alkyl;

R⁷ is hydrogen, C₁-C₂₄-alkyl, R⁶—C(═O)—, R⁶—NH—C(═O)—;

A is —C(═O)—O, —C(═O)—B—C(═O)—O, —CH₂—CH(—OH)—B—CH(—OH)—CH₂—O, —C(═O)—NH—B—NH—C(═O)—;

B is —(CH₂)_(t)—, arylene, optionally substituted;

R³⁰, R³¹ are hydrogen, C₁-C₂₄-alkyl, C₁-C₂₄-hydroxyalkyl, benzyl orphenyl;

n is 1 when R¹ is not a polyalcohol radical or

n is 1 to 1000 when R¹ is a polyalcohol radical

s=0 to 1000; t=1 to 12; u=1 to 5000; v=0 to 5000; w=0 to 5000;

x=0 to 5000; y=0 to 5000; z=0 to 5000.

Alkyl radicals for R⁶ and R³⁰ and R³¹ which may be mentioned arebranched or unbranched C₁-C₂₄-alkyl chains, preferably methyl, ethyl,n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl,1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl,n-heptyl, 2-ethylhexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl,n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl,n-octadecyl, n-nonadecyl or n-eicosyl.

Preferred representatives of the abovementioned alkyl radicals which maybe mentioned are branched or unbranched C₁-C₁₂—, particularly preferablyC₁-C₆-alkyl chains.

As graft base c1), preference is given to polyalkylene glycols, such as,for example, polyethylene glycols and polypropylene glycols. Particularpreference is given to polyethylene glycols.

The molecular weight of the polyethers c1) is in the range greater than300 (number-average), preferably in the range from 300 to 100 000,particularly preferably in the range from 500 to 50 000, veryparticularly preferably in the range from 800 to 40 000.

Homopolymers of ethylene oxide or copolymers with an ethylene oxidecontent of from 40 to 99% by weight are used advantageously. For theethylene oxide polymers which are preferably to be used, the content ofcopolymerized ethylene oxide is thus 40 to 100 mol %. Suitablecomonomers for these copolymers are propylene oxide, butylene oxide andisobutylene oxide. Copolymers of ethylene oxide and propylene oxide,copolymers of ethylene oxide and butylene oxide, and copolymers ofethylene oxide, propylene oxide and at least one butylene oxide, forexample, are suitable. The ethylene oxide content in the copolymers ispreferably 40 to 99 mol %, the propylene oxide content is 1 to 60 mol %and the content of butylene oxide in the copolymers is 1 to 30 mol %. Aswell as straight-chain types, it is also possible to use branchedhomopolymers or copolymers as polyether-containing compounds c1).

Branched polymers can be prepared by adding ethylene oxide andoptionally also propylene oxide and/or butylene oxides onto, forexample, polyalcohol radicals, e.g. onto pentaerythritol, glycerol oronto sugar alcohols, such as D-sorbitol and D-mannitol, and also ontopolysaccharides, such as cellulose and starch. The alkylene oxide unitsmay be randomly distributed or be present in the form of blocks withinthe polymer.

It is, however, also possible to use polyesters of polyalkylene oxidesand aliphatic or aromatic dicarboxylic acids, e.g. oxalic acid, succinicacid, adipic acid and terephthalic acid with molar masses of from 1500to 25 000, as described, for example, in EP-A-0 743 962, aspolyether-containing compound. Furthermore, it is also possible to usepolycarbonates by reacting polyalkylene oxides with phosgene orcarbonates, such as, for example, diphenyl carbonate, and alsopolyurethanes by reacting polyalkylene oxides with aliphatic andaromatic diisocyanates.

As polyether c1), particular preference is given to polymers of theformula III with an average molecular weight of from 300 to 100 000(number-average), in which the variables, independently of one another,have the following meanings:

R⁴ is hydrogen, C₁-C₁₂-alkyl, R⁹—C(═O)—, R⁹—NH—C(═O)—, polyalcoholradical;

R⁸ is hydrogen, C₁-C₁₂-alkyl, R⁹—C(═O)—, R⁹—NH—C(═O)—;

R⁵ to R⁷ are —(CH₂)₂—, —(CH₂)₃—, —(CH₂)₄—, —CH₂—CH(R⁹)—,—CH₂—CHOR¹⁰—CH₂—;

R⁹ is C₁-C₁₂-alkyl;

R¹⁰ is hydrogen, C₁-C12-alkyl, R⁹—C(═O)—, R⁹—NH—C(═O)—;

n=1 to 8; s=0; u=2 to 2000; v=0 to 2000; w=0 to 2000.

As polyether c1), very particular preference is given to polymers of theformula III with an average molecular weight of from 500 to 50 000(number-average), in which the variables, independently of one another,have the following meanings:

R⁴ is hydrogen, C₁-C₆-alkyl, R⁹—C(═O)—, R⁹—NH—C(═O)—;

R⁸ is hydrogen, C₁-C₆-alkyl, R⁹—C(═O)—, R⁹—NH—C(═O)—;

R⁵ to R⁷ are —(CH₂)₂—, —(CH₂)₃—, —(CH₂)₄—, —CH₂—CH(R⁹)—,—CH₂—CHOR¹⁰—CH₂—;

R⁹ is C₁-C₆-alkyl;

R¹⁰ is hydrogen, C₁-C₆-alkyl, R⁹—C(═O)—, R⁹—NH—C(═O)—;

n=1; s=0; u=5 to 500; v=0 to 500; w=0 to 500.

However, the polyethers c1) used may also be silicone derivatives.Suitable silicone derivatives are the compounds known under the INCIname dimethicone copolyols or silicone surfactants, such as, forexample, those available under the trade names Abil™ (T. Goldschmidt),Alkasil™ (Rhône-Poulenc), Silicone Polyol Copolymer™ (Genesee), Belsil™(Wacker), Silwet™ (Witco, Greenwich, Conn., USA) or Dow Corning (DowCorning). These include compounds with the CAS numbers 64365-23-7;68937-54-2; 68938-54-5; 68937-55-3.

Silicones are generally used in hair cosmetics to improve the feel. Theuse of polyether-containing silicone derivatives as polyethers c1) inthe polymers according to the invention can therefore additionally leadto an improvement in the feel of the hair.

Preferred representatives of such polyether-containing siliconederivatives are those which comprise the following structural elements:

where:

-   -   R¹⁵ is an organic radical containing 1 to 40 carbon atoms and        which can comprise amino, carboxylic acid or sulfonate groups,        or for the case e=0, is also the anion of an inorganic acid,        and where the radicals R¹¹ may be identical or different, and        either originate from the group of aliphatic hydrocarbons having        1 to 20 carbon atoms, are cyclic aliphatic hydrocarbons having 3        to 20 carbon atoms, are of an aromatic nature or are identical        to R¹², where:        with the proviso that at least one of the radicals R¹¹, R¹² or        R¹³ is a polyalkylene oxide-containing radical according to the        abovementioned definition and f is an integer from 1 to 6, a and        b are integers such that the molecular weight of the        polysiloxane block is between 300 and 30 000, c and d may be        integers between 0 and 50, with the proviso that the sum of c        and d is greater than 0, and e is 0 or 1.

Preferred radicals R¹² and R¹⁶ are those in which the sum c+d is between5 and 30.

The groups R¹¹ are preferably chosen from the following group: methyl,ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, decyl,dodecyl and octadecyl, cycloaliphatic radicals, specifically cyclohexyl,aromatic groups, specifically phenyl or naphthyl, mixedaromatic-aliphatic radicals such as benzyl or phenylethyl and tolyl andxylyl and R¹⁶.

Particularly suitable radicals R¹⁴ are those in which in the case whereR¹⁴═—(CO)_(e)—R¹⁵, R¹⁵ is a desired alkyl, cycloalkyl or aryl radicalwhich has between 1 and 40 carbon atoms and which can carry furtherionogenic groups such as NH₂, COOH, SO₃H.

Preferred inorganic radicals R¹⁵ are, for the case e=0, phosphate andsulfate.

Particularly preferred polyether-containing silicone derivatives c-1)are those of the structure:

In addition, homo- and copolymers of polyalkylene oxide-containingethylenically unsaturated monomers, such as, for example, polyalkyleneoxide(meth)acrylates, polyalkylene oxide vinyl ethers, polyalkyleneoxide(meth)acrylamides, polyalkylene oxide allylamides or polyalkyleneoxide vinylamides can also be used as polyethers (c1). It is of coursealso possible to use copolymers of such monomers with otherethylenically unsaturated monomers.

As polyether-containing compounds c1), it is, however, also possible touse reaction products of polyethyleneimines with alkylene oxides. Inthis case, the alkylene oxides used are preferably ethylene oxide,propylene oxide, butylene oxide and mixtures thereof, particularlypreferably ethylene oxide. Polyethyleneimines which can be used arepolymers having number-average molecular weights of from 300 to 20 000,preferably from 500 to 10 000, very particularly preferably from 500 to5 000. The weight ratio between used alkylene oxide andpolyethyleneimine is in the range from 100:1 to 0.1:1, preferably in therange from 50:1 to 0.5:1, very particularly preferably in the range from20:1 to 0.5:1.

Graft Base c2)

As well as at least one compound from the group of polyether-containingcompounds c1), the graft base c) comprises at least one compound fromthe group of polymers c2) which comprise at least 5% by weight ofvinylpyrrolidone units.

Preferably, these polymers used as graft base comprise avinylpyrrolidone content of at least 10% by weight, very particularlypreferably of at least 30% by weight, in particular at least 50% byweight, preferably at least 80% by weight.

Particularly preferred graft bases c) are polyvinylpyrrolidonehomopolymers.

Suitable comonomers of the vinylpyrrolidone for the synthesis of thegraft base (c2) are, for example, N-vinylcaprolactam, N-vinylimidazole,N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole,3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methylsulfate, diallyldimethylammonium chloride, styrene, alkylstyrenes.

Further suitable comonomers for the preparation of the graft base c2)are, for example, monoethylenically unsaturated C₃-C₆-carboxylic acids,such as, for example, acrylic acid, methacrylic acid, crotonic acid,fumaric acid, and esters, amides and nitriles thereof, such as, forexample, methyl acrylate, ethyl acrylate, methyl methacrylate, ethylmethacrylate, stearyl methacrylate, hydroxyethyl acrylate, hydroxypropylacrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate,hydroxypropyl methacrylate, hydroxyisobutyl acrylate, hydroxyisobutylmethacrylate, monomethyl maleate, dimethyl maleate, monoethyl maleate,diethyl maleate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate,maleic anhydride and monoesters thereof, alkylene glycol(meth)acrylates,acrylamide, methacrylamide, N,N-dimethylacrylamide,N-tert-butylacrylamide, acrylonitrile, methacrylonitrile, vinyl ethers,such as, for example, methyl, ethyl, butyl or dodecyl vinyl ethers,cationic monomers, such as dialkylaminoalkyl(meth)acrylates anddialkylaminoalkyl(meth)acrylamides, such as dimethylaminomethylacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate,and the salts of the last-named monomers with carboxylic acids ormineral acids, and the quaternized products.

The graft base c2) is prepared by known processes, for example,solution, precipitation, suspension or emulsion polymerization usingcompounds which form free radicals under the polymerization conditions.The polymerization temperatures are usually in the range from 30 to 200,preferably 40 to 110° C. Suitable initiators are, for example, azo andperoxy compounds, and the customary redox initiator systems, such ascombinations of hydrogen peroxide and compounds which have a reducingaction, for example sodium sulfite, sodium bisulfite, sodiumformaldehyde sulfoxilate and hydrazine. These systems may alsoadditionally comprise small amounts of a heavy metal salt.

The homopolymers and copolymers (graft base C2) have K values of atleast 7, preferably 10 to 250. However, the polymers may have K valuesup to 300. The K values are determined in accordance with H.Fikentscher, Cellulose-Chemie, Volume 13, 58 to 64 and 71 to 74 (1932)in an aqueous solution at 25° C., at concentrations between 0.1% and 5%depending on the K value range.

Component c) (sum of components c1 and c2) is preferably used in anamount of from 10 to 90% by weight, in particular 20 to 70% by weight,preferably 30 to 60% by weight.

In a preferred embodiment of the invention, a mixture comprising atleast one compound c1) polyalkylene glycols and at least one compoundc2) polymers which at least 50% by weight of vinylpyrrolidone units isused as graft base c).

In a preferred embodiment of the invention, a mixture comprising atleast one compound c1) polyalkylene glycols and at least one compoundc2) polymers which at least 50% by weight of vinylpyrrolidone units isused as graft base c), and the polymerization is carried out in thepresence of a crosslinker d).

In a preferred embodiment of the invention, a mixture comprising atleast one compound c1) polyalkylene glycols and at least one compoundc2) polymers which at least 80% by weight of vinylpyrrolidone units isused as graft base c).

In a preferred embodiment of the invention, a mixture comprising atleast one compound c1) polyalkylene glycols and at least one compoundc2) polymers which at least 80% by weight of vinylpyrrolidone units isused as graft base c), and the polymerization is carried out in thepresence of a crosslinker d).

In a preferred embodiment of the invention, a mixture comprising atleast one compound c1) polyalkylene glycols and at least one compoundc2) polyvinylpyrrolidone homopolymer is used as graft base c).

In a preferred embodiment of the invention, a mixture comprising atleast one compound c1) polyalkylene glycols and at least one compoundc2) polyvinylpyrrolidone homopolymer is used as graft base c), and thepolymerization is carried out in the presence of a crosslinker d).

Component d) is preferably used in an amount of from 0 to 10% by weight,in particular from 0.01 to 10% by weight, in particular 0.05 to 5% byweight, preferably 0.1 to 1.5% by weight.

Preparation of the Graft Polymers

It is of course also possible to copolymerize mixtures of the respectivemonomers from group a), such as, for example, mixtures ofN-vinylformamide and N-vinylacetamide.

Component a) is preferably used in an amount of from 10 to 90% byweight, in particular 20 to 70% by weight, preferably 30 to 60% byweight. In a preferred embodiment, the components a), c) and d) are usedin the following amounts. The individual percentages by weight givenhere always refer to the total sum of components a), c) and d), which isset as 100%. If further possible components are present (e.g. componentsb) and e), then the weights given of these further components arecalculated on the basis of the sum of a) to d), which is set as 100%.

Component a) is preferably used in an amount of from 10 to 90% byweight, in particular 20 to 70% by weight, preferably 30 to 60% byweight.

Component c) is preferably used in in an amount of from 90 to 10% byweight, in particular 70 to 20% by weight, preferably 60 to 30% byweight.

Component d) is preferably used in an amount of from 0 to 10% by weight,in particular 0.01 to 10% by weight, in particular 0.05 to 5% by weight,preferably 0.1 to 1.5% by weight.

Particular preference is given to graft polymers obtainable byfree-radical polymerization of

10 to 90% by weight, in particular 20 to 70% by weight, preferably 30 to60% by weight, of component a)

90 to 10% by weight, in particular 70 to 20% by weight, preferably 60 to30% by weight, of component c)

0 to 10% by weight, preferably 0,01 to 10% by weight, in particular 0.05to 5% by weight, preferably 0.1 to 1.5% by weight, of component d)

with the proviso that the sum of a), c) and d) adds up to 100%.

If further components are present, these are preferably present in thefollowing amounts (based on the 100% of the sum of a), c) and d))

-   -   0-60% by weight, preferably 0 to 40% by weight, preferably 0-25%        by weight, particularly preferably 0-15% by weight, of component        b)    -   0-5% by weight, preferably 0-2.5% by weight, particularly        preferably 0-1.5% by weight, of component e).

Preference is given to graft polymers obtainable by free-radical graftcopolymerization of

-   -   a) 10-90% by weight, in particular 20 to 80% by weight, of at        least one open-chain N-vinylamide compound of the formula I and    -   b) 0-60% by weight, in particular 0-25% by weight of one or more        further copolymerizable monomers onto    -   c) 90-10% by weight, in particular 80 to 20% by weight, of a        water-soluble or water-dispersible polymeric graft base c).

Preference is given to graft polymers obtainable by free-radical graftcopolymerization of

-   -   a) 10-90% by weight, in particular 20 to 80% by weight, of at        least one open-chain N-vinylamide compound of the formula I and    -   b) 0-60% by weight, in particular 0-25% by weight, of one or        more further copolymerizable monomers onto    -   c) 90-10% by weight, in particular 80 to 20% by weight, of a        water-soluble or water-dispersible polymeric graft base c)    -   d) 0-10% by weight, in particular 0.01-10% by weight, of a        crosslinker d).

Very particular preference is given to graft polymers obtainable byfree-radical graft copolymerization of

-   -   a) 30-60% by weight of at least one open-chain N-vinyl-amide        compound of the formula I and    -   b) 0-40% by weight of one or more further copolymerisable        monomers onto    -   c) 60-30% by weight of one or more water-soluble or        water-dispersible polymeric graft base c)    -   d) 0.05-5% by weight of a crosslinker d).

To prepare the polymers, the monomers of component a) and optionally ofcomponent b) may be polymerized in the presence of the graft basec)[=c1) and c2)] either using initiators which form free radicals, or bythe action of high-energy radiation, which is also intended to mean theaction of high-energy electrons.

Initiators which can be used for the free-radical polymerization are theperoxo and/or azo compounds customary for this purpose, for examplealkali metal or ammonium peroxydisulfates, diacetyl peroxide, dibenzoylperoxide, succinyl peroxide, di-tert-butyl peroxide, tert-butylperbenzoate, tert-butyl perpivalate, tert-butylperoxy-2-ethyl hexanoate,tert-butyl permaleate, cumene hydroperoxide, diisopropylperoxydicarbamate, bis(o-toloyl) peroxide, didecanoyl peroxide,dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate,tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide,azobisisobutyronitrile, azobis(2-amidinopropane) dihydrochloride or2,2′-azobis(2-methylbutyronitrile). Also suitable are initiator mixturesor redox initiator systems, such as, for example, ascorbic acid/iron(II)sulfate/sodium peroxodisulfate, tert-butyl hydroperoxide/sodiumdisulfite, tert-butyl hydroperoxide/sodium hydroxymethanesulfinate.

Preference is given to using organic peroxides.

The polymerization can also be carried out by the action of ultravioletradiation, optionally in the presence of UV initiators. For thepolymerization under the action of UV rays, use is made of the suitablephotoinitiators and/or or sensitizers customary for this purpose. Theseare, for example, compounds such as benzoin and benzoin ether,α-methylbenzoin or α-phenylbenzoin. It is also possible to use “tripletsensitizers”, such as benzyl diketals. The UV radiation sources usedare, for example, in addition to high-energy UV lamps, such as carbonarc lamps, mercury vapor lamps or xenon lamps, also low-UV lightsources, such as fluorescent tubes with a high blue component.

The amounts of initiator or initiator mixtures used, based on monomerused, are between 0.01 and 10% by weight, preferably between 0.1 and 5%by weight.

The polymerization is carried out in the temperature range from 40 to200° C., preferably in the range from 50 to 140° C., particularlypreferably in the range from 60 to 110° C. It is usually carried outunder atmospheric pressure, but can also be carried out under reduced orincreased pressure, preferably between 1 and 5 bar.

The polymerization can, for example, be carried out as solutionpolymerization, bulk polymerization, emulsion polymerization, inverseemulsion polymerization, suspension polymerization, inverse suspensionpolymerization or precipitation polymerization, without the possiblemethods being limited thereto.

In the case of bulk polymerization, the procedure may involve dissolvingthe graft base c) in at least one monomer of group a) and possibly othercomonomers of group b) and, after the addition of a polymerizationinitiator, fully polymerizing the mixture. The polymerization can alsobe carried out semicontinuously by firstly introducing some, e.g. 10%,of the mixture to be polymerized comprising the graft base c), at leastone monomer of group a), possibly other comonomers of group b) andinitiator, heating the mixture to the polymerization temperature and,after the polymerization has started, adding the remainder of themixture to be polymerized in accordance with the progress of thepolymerization. The polymers can also be obtained by initiallyintroducing the graft base c) into a reactor, heating it to thepolymerization temperature and adding at least one monomer of group a),possibly other comonomers of group b) and polymerization initiatoreither in one portion, step by step or, preferably, continuously, andpolymerizing.

If desired, the above-described polymerization can also be carried outin a solvent. Suitable solvents are, for example, alcohols, such asmethanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol,tert-butanol, n-hexanol and cyclohexanol, and glycols, such as ethyleneglycol, propylene glycol and butylene glycol, and the methyl or ethylethers of dihydric alcohols, diethylene glycol, triethylene glycol,glycerol and dioxane. The polymerization can also be carried out inwater as solvent. In this case, the initial charge is a solution which,depending on the amount of monomers of component a) added, is soluble inwater to a greater or lesser degree. In order to convert water-insolubleproducts, which can form during the polymerization, into solution, it ispossible, for example, to add organic solvents, such as monohydricalcohols having from 1 to 3 carbon atoms, acetone or dimethylformamide.However, in the case of polymerization in water, it is also possible toconvert the water-insoluble polymers into a finely divided dispersion byaddition of customary emulsifiers or protective colloids, e.g. polyvinylalcohol.

The emulsifiers used are, for example, ionic or nonionic surfactantswhose HLB value is in the range from 3 to 13. The definition of the HLBvalue can be found in the publication by W. C. Griffin, J. Soc. CosmeticChem., Volume 5, 249 (1954).

The amount of surfactants, based on the graft polymer, is 0.1 to 10% byweight. Using water as solvent gives solutions or dispersions of thepolymers. If solutions of the polymer are prepared in an organic solventor in mixtures of an organic solvent and water, then, per 100 parts byweight of the polymer, 5 to 2 000, preferably 10 to 500, parts by weightof the organic solvent or of the solvent mixture are used.

The graft copolymers according to the invention can be hydrolyzed afterthe polymerization. The hydrolysis produces a cationic group in thepolymer. This may lead to increased solubility in water and improvedconditioning properties in cosmetic applications.

From the above-described graft copolymers arise, by partial or completeelimination of the formyl groups or of the C₁-C₆-alkyl-C═O— groups fromthose open-chain N-vinylamides (IV) incorporated into the polymer, withthe formation of amine and/or ammonium groups, units of the formula (V)

In the formulae (IV) and (V), the substituents R¹ and R² are each asdefined above. Depending on the reaction conditions chosen during thehydrolysis, either partial or complete hydrolysis of the units (IV) isachieved.

If, in addition to the hydrolysis-insensitive vinylpyrrolidone units,the graft base also comprises comonomers which are hydrolysis-sensitive,such as, for example, vinyl acetate or acrylamide, then hydrolysis alsotakes place in the graft base. Thus, vinyl acetate reacts to give vinylalcohol groups, and acrylamide reacts to give acrylic acid groups.

Suitable hydrolysis agents are mineral acids, such as hydrogen halides,which can be used in gaseous form or in aqueous solution. Preference isgiven to using hydrochloric acid, sulfuric acid, nitric acid andphosphoric acid, and organic acids, such as C₁-C₅-carboxylic acids andaliphatic or aromatic sulfonic acids. 0.05 to 2 mol equivalents,preferably 1 to 1.5 mol equivalents, of an acid are required per formylgroup equivalent which is to be eliminated from the copolymerized units(IV).

The hydrolysis of the copolymerized units of the structure (IV) can alsobe carried out using bases, e.g. metal hydroxides, in particular alkalimetal and alkaline earth metal hydroxides. Preference is given to usingsodium hydroxide or potassium hydroxide. The hydrolysis can optionallyalso be carried out in the presence of ammonia or amines.

The hydrolysis in the acidic or in the alkaline pH range takes place,for example, at temperatures of from 30 to 170, preferably 50 to 120° C.It is complete after about 2 to 8 hours, preferably 3 to 5 hours. Afterthese reaction times, degrees of hydrolysis of the units of thecopolymerized monomers of the formula (I) of from 1 to 100% areachieved. A particularly successful procedure has proven to be one inwhich the bases or acids are added in aqueous solution for thehydrolysis. After the hydrolysis, a neutralization is generally carriedout, such that the pH of the hydrolyzed polymer solution is 2 to 8,preferably 3 to 7. Neutralization is required if a continuation of thehydrolysis of partially hydrolyzed polymers is to be avoided or delayed.The hydrolysis can also be carried out using enzymes.

The polymers prepared in this way can then be cationized by reaction ofhydroxyl and/or amino functions present in the polymer with epoxides ofthe formula X(R³¹═C₁ to C₄₀ alkyl).

For this, the hydroxyl groups of the polyvinyl alcohol units andvinylamine units, formed by hydrolysis of vinylformamide, can preferablybe reacted with the epoxides. The epoxides of the formula X can also beproduced in situ by reaction of the corresponding chlorohydrins withbases, for example sodium hydroxide.

Preference is given to using 2,3-epoxypropyltrimethylammonium chlorideor 3-chloro-2-hydroxypropyltrimethylammonium chloride.

The K values of the polymers should be in the range from 10 to 300,preferably 25 to 250, particularly preferably 25 to 200, veryparticularly preferably in the range from 30 and 150. The K valuedesired in each case can be adjusted in a manner known per se throughthe composition of the feed substances. The K values are determined inaccordance with Fikentscher, Cellulosechemie, Vol. 13, pp. 58 to 64, and71 to 74 (1932) in N-methylpyrrolidone at 25° C. and polymerconcentrations which, depending on the K value range, are between 0.1%by weight and 5% by weight.

To remove solvents, the polymer solutions can be steam-distilled.Following steam distillation, aqueous solutions or dispersions areobtained depending on the choice of components a-c.

The graft polymers obtained can also be subsequently crosslinked byreacting the hydroxyl groups or amino groups in the polymer with atleast bifunctional reagents. In the case of low degrees of crosslinking,water-soluble products are obtained, and in the case of high degrees ofcrosslinking, water-swellable or insoluble products are obtained.

For example, the polymers according to the invention can be reacted withdialdehydes and diketones, e.g. glyoxal, glutaraldehyde,succindialdehyde or terephthalaldehyde. Also suitable are aliphatic oraromatic carboxylic acids, for example maleic acid, oxalic acid, malonicacid, succinic acid or citric acid, or carboxylic acid derivatives, suchas carboxylic esters, anhydrides or halides. Also suitable arepolyfunctional epoxides, e.g. epichlorohydrin, glycidyl methacrylate,ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether or1,4-bis(glycidyloxy)benzene. Also suitable are diisocyanates, forexample hexamethylene diisocyanate, isophorone diisocyanate,methylenediphenyl diisocyanate, toluylene diisocyanate ordivinylsulfone.

Also suitable are inorganic compounds, such as boric acid or boric acidsalts, for example sodium metaborate, borax (disodium tetraborate), andsalts of polyvalent cations, e.g. copper(II) salts, such as copper(II)acetate, or zinc, aluminum, titanium salts.

Boric acid and/or boric acid salts, such as sodium metaborate ordisodium tetraborate, are preferably suitable for the subsequentcrosslinking. In this connection, boric acid and/or boric acid saltscan, preferably as salt solutions, be added to the solutions of thepolymers according to the invention. Preference is given to adding boricacid and/or boric acid salts to the aqueous polymer solutions.

The boric acid and/or boric acid salts can be added to the polymersolutions directly after preparation. It is, however, also possible toadd the boric acid and/or boric acid salts subsequently to the cosmeticformulations containing the polymers according to the invention, or toadd them during the preparation process of the cosmetic formulations.The proportion of boric acid and/or boric acid salts, based on thepolymers according to the invention, is 0 to 15% by weight, preferably 0to 10% by weight, particularly preferably 0 to 5% by weight.

The graft polymer solutions and dispersions can be converted into powderform by a variety of drying methods, such as, for example, spray drying,fluidized spray drying, drum drying or freeze drying. The drying methodused with preference is spray drying. The dry polymer powder obtained inthis way can be used to prepare an aqueous solution or dispersion again,by dissolution or redispersion in water. Conversion into powder form hasthe advantage of better storability, easier transportation, and a lowerpropensity for microbial attack.

The graft copolymers according to the invention are highly suitable foruse in cosmetic formulations. They are suitable in particular asconditioning agents and as thickeners.

The graft polymers according to the invention are suitable as stylingagents and/or conditioning agents in hair cosmetic preparations, such ashair cures, hair lotions, hair rinses, hair emulsions, split-end fluids,neutralizers for permanent waves, “hot-oil treatment” preparations,conditioners, setting lotions or hairsprays. Depending on the field ofapplication, the hair cosmetic preparations can be applied as spray,foam, gel, gel spray or mousse.

The hair cosmetic formulations according to the invention comprise, in apreferred embodiment

-   -   a) 0.01-20% by weight of the graft polymer according to the        invention    -   b) 20-99.99% by weight of water and/or alcohol    -   c) 0-79.5% by weight of further constituents.

Alcohol is to be understood as meaning all alcohols customary incosmetics, e.g. ethanol, isopropanol, n-propanol.

Further constituents are to be understood as meaning the additivescustomary in cosmetics, for example propellants, antifoams,interface-active compounds, i.e. surfactants, emulsifiers, foam formersand solubilizers. The interface-active compounds used can be anionic,cationic, amphoteric or neutral. Further customary constituents can alsobe, for example, preservatives, perfume oils, opacifiers, activeingredients, UV filters, care substances such as panthenol, collagen,vitamins, protein hydrolyzates, alpha- and beta-hydroxycarboxylic acids,stabilizers, pH regulators, dyes, viscosity regulators, gel formers,salts, moisturizers, refatting agents and further customary additives.

These also include all styling and conditioning polymers known incosmetics which can be used in combination with the polymers accordingto the invention, in cases where very specific properties are to be set.

Suitable traditional hair cosmetic polymers are, for example, anionicpolymers. Such anionic polymers are homo- and copolymers of acrylic acidand methacrylic acid or salts thereof, copolymers of acrylic acid andacrylamide and salts thereof; sodium salts of polyhydroxycarboxylicacids, water-soluble or water-dispersible polyesters, polyurethanes(Luviset™ P.U.R.) and polyureas. Particularly suitable polymers arecopolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (e.g.Luvimer™ 100P), copolymers of N-tert-butylacrylamide, ethyl acrylate,acrylic acid (Ultrahold™ 8, strong), copolymers of vinyl acetate,crotonic acid and optionally other vinyl esters (e.g. Luviset™ grades),maleic anhydride copolymers, optionally reacted with alcohols, anionicpolysiloxanes, e.g. carboxy-functional ones, copolymers ofvinylpyrrolidone, t-butyl acrylate, methacrylic acid (e.g. Luviskol™VBM).

Very particularly preferred anionic polymers are acrylates with an acidnumber greater than or equal to 120 and copolymers of t-butyl acrylate,ethyl acrylate or methacrylic acid.

Other suitable hair cosmetic polymers are cationic polymers with thename polyquaternium according to INCI, e.g. copolymers ofvinylpyrrolidone/N-vinylimidazolium salts (Luviquat™ FC, Luviquat™ HM,Luviquat™ MS, Luviquat™ Care), copolymers ofN-vinylpyrrolidone/dimethylaminoethyl methacrylate, quaternized withdiethyl sulfate (Luviquat™ PQ 11), copolymers ofN-vinylcaprolactam-N-vinylpyrrolidone/N-vinylimidazolium salts(Luviquat™ Hold); cationic cellulose derivatives (polyquaternium-4 and-10), acrylamide copolymers (polyquaternium-7).

Other suitable hair cosmetic polymers are also neutral polymers such aspolyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinylacetate and/or vinyl propionate, polysiloxanes, polyvinylcaprolactam andcopolymers with N-vinylpyrrolidone, polyethyleneimines and saltsthereof, polyvinylamines and salts thereof, cellulose derivatives,polyaspartic acid salts and derivatives.

To establish certain properties, the preparations can also additionallycomprise conditioning substances based on silicone compounds. Suitablesilicone compounds are, for example, polyalkylsiloxanes,polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes, siliconeresins or dimethicone copolyols (CTFA) and amino-functional siliconecompounds such as amodimethicones (CTFA).

The graft polymers according to the invention are suitable in particularas setting agents in hairstyling preparations, in particular hairsprays(aerosol sprays and pump sprays without propellant gas) and hair foams(aerosol foams and pump foams without propellant gas).

In a preferred embodiment, these preparations comprise

-   -   a) 0,1-10% by weight of the graft polymer according to the        invention    -   b) 20-99.9% by weight of water and/or alcohol    -   c) 0-70% by weight of a propellant    -   d) 0-20% by weight of further constituents

Propellants are the propellants customarily used for hairsprays andaerosol foams. Preference is given to mixtures of propane/butane,pentane, dimethyl ether, 1,1-difluoroethane (HFC-152 a), carbon dioxide,nitrogen or compressed air.

A formulation for aerosol hair foams preferred according to theinvention comprises

-   -   a) 0.1-10% by weight of the graft copolymer according to the        invention    -   b) 55-94.8% by weight of water and/or alcohol    -   c) 5-20% by weight of a propellant    -   d) 0.1-5% by weight of an emulsifier    -   e) 0-10% by weight of further constituents

The emulsifiers which may be used are all emulsifiers customarily usedin hair foams. Suitable emulsifiers may be nonionic, cationic oranionic.

Examples of nonionic emulsifiers (INCI nomenclature) are laureths, e.g.laureth-4; ceteths, e.g. ceteth-1, polyethylene glycol cetyl ether;ceteareths, e.g. ceteareth-25, polyglycol fatty acid glycerides,hydroxylated lecithin, lactyl esters of fatty acids, alkylpolyglycosides.

Examples of cationic emulsifiers arecetyldimethyl-2-hydroxyethylammonium dihydrogenphosphate, cetyltrimoniumchloride, cetyltrimonium bromide, cocotrimonium methyl sulfate,quaternium-1 to x (INCI).

Anionic emulsifiers can, for example, be chosen from the group of alkylsulfates, alkyl ether sulfates, alkylsulfonates, alkylarylsulfonates,alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyltaurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates,alkyl ether carboxylates, alpha-olefinsulfonates, in particular thealkali metal and alkaline earth metal salts, e.g. sodium, potassium,magnesium, calcium, and ammonium and triethanolamine salts. The alkylether sulfates, alkyl ether phosphates and alkyl ether carboxylates canhave from 1 to 10 ethylene oxide or propylene oxide units, preferably 1to 3 ethylene oxide units, in the molecule.

A preparation suitable according to the invention for styling gels may,for example, have the following composition:

-   -   a) 0.1-10% by weight of the graft polymer according to the        invention    -   b) 60-99.85% by weight of water and/or alcohol    -   c) 0.05-10% by weight of a gel former    -   d) 0-20% by weight of further constituents

The gel formers which can be used are all gel formers customary incosmetics. These include slightly crosslinked polyacrylic acid, forexample carbomer (INCI), cellulose derivatives, e.g.hydroxypropylcellulose, hydroxyethylcellulose, cationically modifiedcelluloses, polysaccharides, e.g. xanthum gum, caprylic/caprictriglycerides, sodium acrylates copolymer, polyquaternium-32 (and)paraffinum liquidum (INCI), sodium acrylates copolymer (and) paraffinumliquidum (and) PPG-1 trideceth-6, acrylamidopropyl trimoniumchloride/acrylamide copolymer, steareth-10 allyl ether acrylatescopolymer, polyquaternium-37 (and) paraffinum liquidum (and) PPG-1trideceth-6, polyquaternium 37 (and) propylene glycol dicapratedicaprylate (and) PPG-1 trideceth-6, polyquaternium-7,polyquaternium-44.

The polymers according to the invention can also be used in shampooformulations as setting and/or conditioning agents. Polymers with acationic charge are in particular suitable as conditioning agents.

Preferred shampoo formulations comprise

-   -   a) 0.01-10% by weight of the graft polymer according to the        invention    -   b) 25-94.99% by weight of water    -   c) 5-50% by. weight of surfactants    -   d) 0-5% by weight of a further conditioning agent    -   e) 0-10% by weight of further cosmetic constituents

In the shampoo formulations it is possible to use all anionic, neutral,amphoteric or cationic surfactants customarily used in shampoos.

Suitable anionic surfactants are, for example, alkyl sulfates, alkylether sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates,alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acylisethionates, alkyl phosphates, alkyl ether phosphates, alkyl ethercarboxylates, alpha-olefinsulfonates, in particular the alkali metal andalkaline earth metal salts, e.g. sodium, potassium, magnesium, calciumand ammonium and triethanolamine salts. The alkyl ether sulfates, alkylether phosphates and alkyl ether carboxylates can have from 1 to 10ethylene oxide or propylene oxide units, preferably 1 to 3 ethyleneoxide units, in the molecule.

Suitable examples are sodium lauryl sulfate, ammonium lauryl sulfate,sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodiumlauroyl sarcosinate, sodium oleyl succinate, ammonium laurylsulfosuccinate, sodium dodecylbenzenesulfonate, triethanolaminedodecylbenzenesulfonate.

Suitable amphoteric surfactants are, for example, alkylbetaines,alkylamidopropylbetaines, alkylsulfobetaines, alkyl glycinates, alkylcarboxyglycinates, alkyl amphoacetates or -propionates, alkylamphodiacetates or -dipropionates. It is possible, for example, to usecocodimethylsulfopropylbetaine, laurylbetaine, cocamidopropylbetaine orsodium cocamphopropionate.

Examples of suitable nonionic surfactants are the reaction products ofaliphatic alcohols or alkylphenols having 6 to 20 carbon atoms in thealkyl chain, which may be linear or branched, with ethylene oxide and/orpropylene oxide. The amount of alkylene oxide is about 6 to 60 mol permole of alcohol. Also suitable are alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, alkylpolyglycosides or sorbitan ether esters.

In addition, the shampoo formulations may comprise customary cationicsurfactants, such as, for example, quaternary ammonium compounds, forexample cetyltrimethylammonium chloride.

In the shampoo formulations it is possible to use customary conditioningagents in combination with the polymers according to the invention toachieve certain effects. These agents include, for example, cationicpolymers with the INCI name polyquaternium, in particular copolymers ofvinylpyrrolidone/N-vinylimidazolium salts (Luviquat™ FC, Luviquat™ HM,Luviquat™ MS, Luviquat™ Care), copolymers ofN-vinylpyrrolidone/dimethylaminoethyl methacrylate, quaternized withdiethyl sulfate (Luviquat™ PQ 11), copolymers ofN-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazolium salts(Luviquat™ Hold); cationic cellulose derivatives (polyquaternium-4 and-10), acrylamide copolymers (polyquaternium-7). It is also possible touse protein hydrolyzates, and conditioning substances based on siliconecompounds, for example polyalkylsiloxanes, polyarylsiloxanes,polyarylalkylsiloxanes, polyether siloxanes or silicone resins. Furthersuitable silicone compounds are dimethicone copolyols (CTFA) andamino-functional silicone compounds such as amodimethicones (CTFA).

The graft polymers according to the invention can be preparedanalogously to the following examples.

EXAMPLES Synthesis Examples Example 1

60.0 g of polyethylene glycol having an average molecular weight of 4000(Pluriol E 4000, BASF Aktiengesellschaft), 15 g of polyvinylpyrrolidone(K value 30), 180 g of distilled water, 2.8 g of 75% strength phosphoricacid and 2.8 g of 50% strength sodium hydroxide solution are introducedinto a stirred reactor with nitrogen inlet, reflux condenser andmetering device, and are refluxed under nitrogen. Under reflux, 297.1 gof vinylformamide are metered in over 1.5 hours and 10 g of tert-butylperoctoate in 32 g of triethylene glycol monomethyl ether are metered inover 2 hours, and the mixture is further polymerized to completion atthis temperature for 1.5 hours. Since the reaction mixture becomeshighly viscous over the course of the reaction, 250 g of distilled waterare metered in 45 minutes after the start of polymerization over thecourse of 1.5 hours. When the reaction is complete, the mixture isdiluted with 500 g of distilled water.

Example 2 Hydrolysis of Example 1

500 g of the solution obtained in Example 1 are heated to 80° C. with100 g of distilled water and 1 g of sodium pyrosulfite. After theaddition of 33 g of 25% strength sodium hydroxide solution, the mixtureis stirred for 3 hours at 80° C. After cooling, the mixture is adjustedto pH 8 using 15 g of 38% strength hydrochloric acid.

Example 3

120 g of polyethylene glycol having an average molecular weight of 1500(Pluriol E 1500, BASF Aktiengesellschaft) and 43 g ofpolyvinylpyrrolidone (K value 90) are introduced into a stirred reactorwith nitrogen inlet, reflux condenser and metering device, and meltedunder nitrogen. Over the course of one hour, 18.5 g of N-vinylformamideand 1.35 g of tert-butyl peroctoate in 16.1 g of triethylene glycolmonomethyl ether are metered in over the course of 1.5 hours at 90° C.is afterpolymerized for one hour. During the afterpolymerization, thereaction mixture is diluted with distilled water.

Example 4

100 g of polyethylene glycol having an average molecular weight of 9000(Pluriol E 9000, BASF Aktiengesellschaft) and 27 g ofpolyvinylpyrrolidone (K value 17) are melted in a stirred reactor withnitrogen inlet, reflux condenser and metering device. 54.6 g ofN-vinylformamide and 70 mg of butanediol divinyl ether are metered inover the course of one hour, and 1.88 g of tert-butyl peroctoate in 16.1g of triethylene glycol monomethyl ether are metered in over the courseof 1.5 hours at 90° C., and then the mixture is afterpolymerized for onehour at this temperature. During the afterpolymerization, the mixture isdiluted with distilled water.

Example 5

65 g of PEG-PPG block copolymer having an average molecular weight of8000 (Lutrol F 68, BASF Aktiengesellschaft), 7 g ofpolyvinylpyrrolidone/vinyl acetate copolymer (Luviskol™ VA 64 BASFAktiegesellschaft), 180 g of distilled water, 2.8 g of 75% strengthphosphoric acid and 2.8 g of 50% strength sodium hydroxide solution areintroduced into a stirred reactor with nitrogen inlet, reflux condenserand metering device and heated to reflux under nitrogen. Under reflux,410 g of vinylformamide are metered in over the course of 1.5 hours, and10 g of tert-butyl peroctoate in 32 g of triethylene glycol monomethylether are metered in over 2 hours and the mixture is further polymerizedto completion for 1.5 hours at this temperature. Since the reactionmixture becomes highly viscous in the course of the reaction, 250 g ofdistilled water are metered in 45 minutes after the start ofpolymerization over the course of 1.5 hours. When the reaction iscomplete, the mixture is diluted with 500 g of distilled water.

Example 6

Example 6 was carried out analogously to Example 5 using 72 g ofalkylpolyethlene glycol with an average molecular weight of 3500(Pluriol A 2000, BASF Aktiengesellschaft) instead of PEG-PPG blockcopolymer.

Example 7

Example 7 was carried out analogously to Example 5, using 103 g ofpolyethylene glycol with an average molecular weight of 20 000 insteadof PEG-PPG block copolymer.

Example 8

Example 8 was carried out analogously to Example 5 using 137 g ofpolyethylene glycol with an average molecular weight of 35 000 insteadof PEG-PPG block copolymer.

Example 9

Example 9 was carried out analogously to Example 5 using 103 g ofpolyethylene glycol with an average molecular weight of 20 000 insteadof PEG-PPG block copolymer.

Example 10

Example 10 was carried out analogously to Example 5 using 202 g ofdimethicone copolyol (Belsil DMC 6031 ™, Wacker Chemie GmbH) instead ofPEG-PPG block copolymer.

Example 11

Example 11 was carried out analogously to Example 5 using 137 g ofethoxylated polyethyleneimine (prepared from 12.5% of polyethyleneiminewith an average molecular weight of 1400 and 87.5% of ethylene oxide)instead of PEG-PPG block copolymer.

Example 12

300 g of a 21.4% strength solution of polyvinylpyrrolidone having a Kvalue of 85.0 and 140 g of polyethylene glycol with an average molecularweight of 1500 are heated to 80° C. in a gentle stream of nitrogen in astirred reactor with nitrogen inlet, reflux condenser and meteringdevice. Over the course of two hours are then uniformly metered in 91.7g of N-vinylformamide and within 2.5 hours 1.83 g of2,2′-azobis(2-amidinopropane) dihydrochloride dissolved in 98.2 g ofwater. When the monomer feed is complete, the reaction mixture isdiluted with 239 g of water. The mixture is then afterpolymerized for 30minutes, the temperature is increased to 85° C. and, with the additionof 0.9 g of 2,2′-azobis(2-amidinopropane)dihydrochloride, the mixture ispolymerized to completion for a further hour.

Example 13

35 g of a 30.3% strength solution of polyvinylpyrrolidone having a Kvalue of 30, 120 g of polyethylene glycol with an average molecularweight of 6000, 451.5 g of water, 0.5 g of sodium dihydrogenphosphateand 50 g of N-vinylformamide are heated to 90° C. in a gentle stream ofnitrogen in a stirred reactor with nitrogen inlet, reflux condenser andmetering device. 1.0 g of 2,2′-azobis(2-amidinopropane)dihydrochlorideis then added in one portion and polymerized for two hours at thereaction temperature. The temperature is then increased to 95° C. and,with the addition of 0.5 g of2,2′-azobis(2-amidinopropane)dihydrochloride, the mixture is polymerizedto completion for a further hour.

Example 14 Hydrolysis of Example 13

450 g of the polymer from Example 13 are heated to 80° C. Over thecourse of one hour, 52 g of 50% strength sodium hydroxide solution areadded dropwise uniformly. The mixture is then stirred for two hours,cooled and adjusted to pH 7 with 62 g of concentrated hydrochloric acid.

Example 15 Hydrolysis of Example 13

450 g of the polymer from Example 13 are heated to 80° C. Over thecourse of one hour, 26 g of 50% strength sodium hydroxide solution areadded dropwise uniformly. The mixture is then stirred for two hours,cooled and adjusted to pH 7 with 31 g of concentrated hydrochloric acid.

Application Examples Example 1 Aerosol Hair Foam Formulation

2.00% copolymer from Example 1

2.00% Luviquat Mono LS (cocotrimonium methyl sulfate)

67.7% water

10.0 propane/butane 3.5 bar (20° C.)

q.s. perfume oil

Example 2

2.00% copolymer from Example 6

2.00% Luviquat Mono LS (cocotrimonium methyl sulfate)

67.7% water

10.0 propane/butane 3.5 bar (20° C.)

q.s. perfume oil

Example 3

Aerosol hair foam: INCI 4.00% copolymer from Example 3 0.20% Cremophor A25 Ceteareth-25 1.00% Luviquat Mono CP Hydroxyethyl CetyldimoniumPhosphate 5.00% ethanol 1.00% panthenol 10.0 propane/butane 3.5 bar (20°C.) q.s. perfume oil ad 100% water

Example 4

Pump foam: INCI 2.00% copolymer from Example 3 2.00% Luviflex Soft(polymer content) 1.20% 2-amino-2-methyl-1-propanol 0.20% Cremophor A 250.10% Uvinul P 25 PEG-25 PABA q.s. preservative q.s. perfume oil ad 100%water

Example 5

Pump spray INCI 4.00% copolymer from Example 4 1.00% panthenol 0.10%Uvinul MS 40 Benzophenone-4 q.s. preservative q.s. perfume oil ad 100%water

Example 6

Pump spray: INCI 4.00% copolymer from Example 3 1.00% panthenol 0.10%Uvinul M 40 Benzophenone-3 q.s. preservative q.s. perfume oil ad 100%ethanol

Example 7

Hairspray: INCI  5.00% copolymer from Example 10  0.10% silicone oil DowCorning DC 190 Dimethicone Copolyol 35.00% dimethyl ether  5.00%n-pentane ad 100% ethanol q.s. perfume oil

Example 8

Hairspray VOC 55%: INCI  3.00% copolymer from Example 4  7.00% LuvisetP.U.R. Polyurethane-1 40.00% dimethyl ether 15.00% ethanol q.s. perfumeoil ad 100% water

Example 9

Hair gel: INCI 0.50% Carbopol 980 Carbomer 3.00% copolymer from Example14 0.10% phytantriol 0.50% panthenol q.s. perfume oil q.s. preservativead 100% water

Example 10

Hair shampoo and shower gel INCI  0.50% copolymer from Example 3 40.00%Texapon NSO Sodium Laureth Sulfate  5.00% Tego Betaine L 7Cocamidopropyl Betaine  5.00% Plantacare 2000 Decyl Glucoside  1.00%propylene glycol q.s. citric acid q.s. preservative  1.00% sodiumchloride ad 100% water

Application Example 11 Skin Cream

A water/oil cream emulsion (skin cream A) according to the invention wasfirstly prepared in accordance with the following formulation: AdditiveINCI % by wt. Cremophor A 6 Ceteareth-6 and Stearyl Alcohol 2.0Cremophor A 25 Ceteareth-25 2.0 Lanette O Cetearyl Alcohol 2.0 Imwitor960 K Glyceryl Stearate SE 3.0 Paraffin oil 5.0 Jojoba oil 4.0 LuvitolEHO Cetearyl Octanoate 3.0 ABIL 350 Dimethicone 1.0 Amerchol L 101Mineral Oil and Lanolin Alcohol 3.0 Veegum Ultra Magnesium AluminumSilicate 0.5 1,2-Propylene glycol Propylene Glycol 5.0 AbiolImidazolidinylurea 0.3 Phenoxyethanol 0.5 D-Panthenol USP 1.0 Polymer(Preparation 0.5 Example 4) Water ad 100

Application Example 12 Shower Gel

A shower gel formulation was prepared according to the followingformulation: Additive INCI % by wt. Texapon NSO Natrium Laureth Sulfate40.0  Tego Betaine L7 Cocamidopropyl Betaine 5.0 Plantacare 2000 DecylGlucoside 5.0 Perfume 0.2 Polymer according to 0.2 Preparation Example 3Euxyl K 100 Benzyl Alcohol, 0.1 Methylchloroisothiazolinone,Methylisothiazolinone D-Panthenol USP 0.5 Citric acid (pH 6-7) q.s. NaCl2.0 Water ad 100

Application Example 13 Humectant Formulation

Formulation A Additive INCI % by wt. a) Cremophor A6 Ceteareth-6 andStearyl Alcohol 2.0 Cremophor A25 Ceteareth-25 2.0 Paraffin oil (high 10viscosity) Lanette O Cetearyl Alcohol 2.0 Stearic acid 3.0 Nip-NipMethylparaben/Propylparaben 70:30 0.5 Abiol Imidazolidinylurea 0.5 b)Polymer 3.0 (Preparation Example 3) Water ad 100.0

The two phases were heated to 80° C., phase a) was stirred into b),homogenized and stirred until cold, and then the mixture was adjusted topH 6 with 10% strength aqueous NaOH solution.

Application Example 14 O/W Cream for Retaining Skin Moisture

Additive % by wt. Glycerol monostearate 2.0 Cetyl alcohol 3.0 Paraffinoil, subliquidum 15.0 Vaseline 3.0 Caprylic/capric triglyceride 4.0Octyldodecanol 2.0 Hydrogenated coconut fat 2.0 Cetyl phosphate 0.4Polymer (Preparation Example 3) 3.0 Glycerol 3.0 Sodium hydroxide q.s.Perfume oil q.s. Preservative q.s. Water ad 100

Application Example 15 O/W Lotion

Additive % by wt. Stearic acid 1.5 Sorbitan monostearate 1.0 Sorbitanmonooleate 1.0 Paraffin oil, subliquidum 7.0 Cetyl alcohol 1.0Polydimethylsiloxane 1.5 Glycerol 3.0 Polymer (Preparation Example 8)0.5 Perfume oil q.s. Preservative q.s. Water ad 100

Application Example 16 W/O Cream

Additive % by wt. PEG-7-hydrogenated castor oil 4.0 Woolwax alcohol 1.5Beeswax 3.0 Triglyceride, liquid 5.0 Vaseline 9.0 Ozokerite 4.0 Paraffinoil, subliquidum 4.0 Glycerol 2.0 Polymer (Preparation Example 2) 2.0Magnesium sulfate*7H₂O 0.7 Perfume oil q.s. Preservative q.s. Water ad100

Application Example 17 Skincare Hydrogel

Additive % by wt. Polymer (Preparation Example 10) 3.0 Sorbitol 2.0Glycerol 3.0 Polyethylene glycol 400 5.0 Ethanol 1.0 Perfume oil q.s.Preservative q.s. Water ad 100

Application Example 18 Hydrodispersion Gel

Additive % by wt. Polymer (Preparation Example 9) 3.0 Sorbitol 2.0Glycerol 3.0 Polyethylene glycol 400 5.0 Triglyceride, liquid 2.0Ethanol 1.0 Perfume oil q.s. Preservative q.s. Water ad 100

Application Example 19 Liquid Soap

Additive % by wt. Coconut fatty acid, potassium salt 15 Potassium oleate3 Glycerol 5 Polymer (Preparation Example 9) 2 Glycerol stearate 1Ethylene glycol distearate 2 Specific additives, complexing agents,fragrances q.s. Water ad 100

Application Example 20 Bodycare Cream

Additive INCI % by wt. Cremophor A6 Ceteareth-6 and Stearyl 2.0% AlcoholCremophor A 25 Ceteareth-25 2.0% Grape (Vitis vinifera) 6.0% seed oilGlyceryl stearate SE 3.0% Cetearyl alcohol 2.0% Dimethicone 0.5% LuvitolEHO Cetearyl Octanoat 8.0% Oxynex 2004 Propylene Glycol, BHT, Ascorbyl0.1% Palmitate, Glyceryl Stearate, Citric Acid Preservative q.s.1,2-Propylene 3.0% glycol USP Glycerol 2.0% EDTA BD 0.1% D-Panthenol USP1.0% Water ad 100 Polymer (Preparation 1.5% Example 7) Tocopherylacetate 0.5%

The formulation had a pH of 6.8. The viscosity (Brookfield [lacuna]

In the application examples below, all the amounts are in % by weight.

Application Example 21 Liquid Make-Up

A 1.70 glyceryl stearate 1.70 cetyl alcohol 1.70 ceteareth-6 1.70ceteareth-25 5.20 caprylic/capric triglyceride 5.20 mineral oil B q.s.preservative 4.30 propylene glycol 2.50 polymer according to PreparationExample 3 59.50  dist. water C q.s. perfume oil D 2.00 iron oxides12.00  titanium dioxide

Preparation:

Heat phase A and phase B separately to 80° C. Then mix phase B intophase A using a stirrer. Cool to 40° C. and add phase C and phase D.Homogenize repeatedly.

Application Example 22 Oil-Free Make-Up

A 0.35 veegum 5.00 butylene glycol 0.15 xanthan gum B 53.0 dist. waterq.s. preservative 0.2 polysorbate-20 1.6tetrahydroxypropylethylenediamine C 1.0 silica 2.0 nylon-12 4.15 mica6.0 titanium dioxide 1.85 iron oxides D 4.0 stearic acid 1.5 glycerylstearate 7.0 benzyl laurate 5.0 isoeicosane q.s. preservative E 1.0dist. water 0.5 panthenol 0.1 imidazolidinylurea 5.0 polymer accordingto Preparation Example 6

Preparation:

Wet phase A with butylene glycol, add to phase B and mix thoroughly.Heat phase AB to 75° C. Pulverize phase C feed substances, add to phaseAB and homogenize thoroughly. Mix feed substances of phase D, heat to80° C. and add to phase ABC. Mix for some time until the mixture ishomogeneous. Transfer the mixture to a vessel fitted with a propellermixer. Mix feed substances of phase E, add to phase ABCD and mixthoroughly.

Application Example 23 Eyeliner

A 40.6  dist. water 0.2 disodium EDTA q.s. preservative B 0.6 xanthangum 0.4 veegum 3.0 butylene glycol 0.2 polysorbate-20 C 15.0  ironoxide/Al powder/silica (e.g. Sicopearl Fantastico Gold ™ from BASF) D10.0  dist. water 30.0  polymer according to Preparation Example 9

Preparation:

Premix phase B. Mix phase B into phase A using a propeller mixer,allowing the thickener to swell. Wet phase C with phase D, add themixture to phase AB and mix thoroughly.

Application Example 24 Shimmering Gel

A 32.6 dist. water 0.1 disodium EDTA 25.0 carbomer (2% strength aqueoussolution) 0.3 preservative B 0.5 dist. water 0.5 triethanolamine C 10.0dist. water 9.0 polymer according to Preparation Example 3 1.0polyquaternium-46 5.0 iron oxide D 15.0 dist. water 1.0 D-panthenol 50 P(panthenol and propylene glycol)

Preparation:

Thoroughly mix the feed substances of phase A in the order given using apropeller mixer. Then add phase B to phase A. Stir slowly until themixture is homogeneous. Thoroughly homogenize phase C until the pigmentsare well distributed. Add phase C and phase D to phase AB and mixthoroughly.

Application Example 25 Waterproof Mascara

A 46.7  dist. water 3.0 Lutrol E 400 (PEG-8) 0.5 xanthan gum q.s.preservative 0.1 imidazolidinylurea 1.3tetrahydroxypropylethylenediamine B 8.0 carnauba wax 4.0 beeswax 4.0isoeicosane 4.0 polyisobutene 5.0 stearic acid 1.0 glyceryl stearateq.s. preservative 2.0 benzyl laurate C 10.0  iron oxide/Al powder/silica(e.g. Sicopearl Fantastico Gold ™ from BASF) E 8.0 polyurethane-1 2.0polymer according to Preparation Example 3

Preparation:

Heat phase A and phase B separately to 85° C. Maintain the temperatureand add phase C to phase A and homogenize until the pigments areuniformly distributed. Add phase B to phase AC and homogenize for 2-3minutes. Then add phase E and stir slowly. Cool the mixture to roomtemperature.

Application Example 26 Sun Protection Gel

Phase A 1.00 PEG-40 hydrogenated castor oil 8.00 octyl methoxycinnamate(Uvinul MC 80 ™ from BASF) 5.00 octocrylene (Uvinul N 539 ™ from BASF)0.80 octyltriazone (Uvinul T 150 ™ from BASF) 2.00butylmethoxydibenzoylmethane (Uvinul BMBM ™ from BASF) 2.00 tocopherylacetate q.s. perfume oil Phase B 2.50 polymer according to PreparationExample 3 0.30 acrylates/C10-30 alkyl acrylate crosspolymer 0.20carbomer 5.00 glycerol 0.20 disodium EDTA q.s. preservative 72.80  dist.water Phase C 0.20 sodium hydroxide

Preparation:

Mix the components of phase A. Allow phase B to swell and stir intophase A with homogenization. Neutralize with phase C and homogenizeagain.

Application Example 27 Sun Protection Emulsion Containing TiO₂ and ZnO₂

Phase A 6.00 PEG-7 hydrogenated castor oil 2.00 PEG-45/dodecyl glycolcopolymer 3.00 isopropyl myristate 8.00 jojoba (Buxus chinensis) oil4.00 octyl methoxycinnamate (Uvinul MC 80) 2.004-methylbenzylidenecamphor (Uvinul MBC 95) 3.00 titanium dioxide,dimethicone 1.00 dimethicone 5.00 zinc oxide, dimethicone Phase B 2.00polymer according to Preparation Example 2 0.20 disodium EDTA 5.00glycerol q.s. preservative 58.80  dist. water Phase C q.s. perfume oil

Preparation:

Heat phases A and B separately to about 85° C. Stir phase B into phase Aand homogenize. Cool to about 40° C., add phase C and briefly homogenizeagain.

Application Example 28 Sun Protection Lotion

Phase A 6.00 octyl methoxycinnamate (Uvinul MC 80 ™ from BASF) 2.504-methylbenzylidenecamphor (Uvinul MBC 95 ™ from BASF) 1.00octyltriazone (Uvinul T 150 ™ from BASF) 2.00butylmethoxydibenzoylmethane (Uvinul BMBM ™ from BASF) 2.00PVP/hexadecene copolymer 5.00 PPG-3 myristyl ether 0.50 dimethicone 0.10BHT, ascorbyl palmitate, citric Acid, glyceryl stearate, propyleneglycol 2.00 cetyl alcohol 2.00 potassium cetyl phosphate Phase B 2.50polymer according to Preparation Example 3 5.00 propylene glycol 0.20disodium EDTA q.s. preservative 63.92  dist. water Phase C 5.00 mineraloil 0.20 carbomer Phase D 0.08 sodium hydroxide Phase E: q.s. perfumeoil

Preparation:

Heat phases A and B separately to about 80° C. Stir phase B into phase Awith homogenization, briefly afterhomogenize. Slurry phase C, stir intophase AB, neutralize with phase D and afterhomogenize. Cool to about 40°C., add phase E, homogenize again.

Application Example 29 Removable Face Mask

Phase A 57.10  dist. water 6.00 polyvinyl alcohol 5.00 propylene glycolPhase B 20.00  alcohol 4.00 PEG-32 q.s perfume oil Phase C 5.00polyquaternium-44 2.70 polymer according to Preparation Example 3 0.20allantoin

Preparation:

Heat phase A to at least 90° C. and stir until dissolved. Dissolve phaseB at 50° C. and stir into phase A. At about 35° C. compensate theethanol loss. Add phase C and stir.

Application Example 30 Face Mask

Phase A 3.00 ceteareth-6 1.50 ceteareth-25 5.00 cetearyl alcohol 6.00cetearyl octanoate 6.00 mineral oil 0.20 bisabolol 3.00 glycerylstearate Phase B 2.00 propylene glycol 5.00 panthenol 2.80 polymeraccording to Preparation Example 3 q.s. preservative 65.00  dist. waterPhase C q.s. perfume oil 0.50 tocopheryl acetate

Preparation:

Heat phase A and B separately to about 80° C. Stir phase B into phase Awith homogenization, briefly afterhomogenize. Cool to about 40° C., addphase C, homogenize again.

Application Example 31 Body Lotion Foam

Phase A 1.50 ceteareth-25 1.50 ceteareth-6 4.00 cetearyl alcohol 10.00 cetearyl octanoate 1.00 dimethicone Phase B 3.00 polymer according toPreparation Example 6 2.00 panthenol 2.50 propylene glycol q.s.preservative 74.50  dist. water Phase C q.s. perfume oil

Preparation:

Heat phases A and B separately to about 80° C. Stir phase B into phase Aand homogenize. Cool to about 40° C., add phase C and briefly homogenizeagain. Containerizing: 90% of active ingredient and 10% propane/butaneat 3.5 bar (20° C.).

Application Example 32 Face Wash for Dry and Sensitive Skin

Phase A 2.50 PEG-40 hydrogenated castor oil q.s. perfume oil 0.40bisabolol Phase B 3.00 glycerol 1.00 hydroxyethyl cetyldimoniumphosphate 5.00 witch hazel (Hamamelis virginiana) distillate 0.50panthenol 0.50 polymer according to Preparation Example 3 q.s.preservative 87.60  dist. water

Preparation:

Dissolve phase A until clear. Stir phase B into phase A.

Application Example 33 Face Wash Paste with Peeling Effect

Phase A 70.00  dist. water 3.00 polymer according to Preparation Example3 1.50 carbomer q.s. preservative Phase B q.s. perfume oil 7.00potassium cocoyl hydrolyzed protein 4.00 cocamidopropylbetaine Phase C1.50 triethanolamine Phase D 13.00  polyethylene (Luwax A ™ from BASF)

Preparation:

Allow phase A to swell. Dissolve phase B until clear. Stir phase B intophase A. Neutralize with phase C. Then stir in phase D.

Application Example 34 Face Soap

Phase A 25.0 potassium cocoate 20.0 disodium cocoamphodiacetate  2.0lauramide DEA  1.0 glycol stearate  2.0 polymer according to PreparationExample 3 50.0 dist. water q.s. citric acid Phase B q.s. preservativeq.s. perfume oil

Preparation:

Heat phase A to 70° C. with stirring until homogeneous. pH to 7.0 to 7.5with citric acid. Cool to 50° C. and add phase B.

Application Example 35 Face Cleansing Milk, O/W Type

Phase A 1.50 ceteareth-6 1.50 ceteareth-25 2.00 glyceryl stearate 2.00cetyl alcohol 10.00  mineral oil Phase B 5.00 propylene glycol q.s.preservative 1.0 polymer according to Preparation Example 3 66.30  dist.water Phase C 0.20 carbomer 10.00  cetearyl octanoate Phase D 0.40tetrahydroxypropylethylenediamine Phase E q.s. perfume oil 0.10bisabolol

Preparation:

Heat phases A and B separately to about 80° C. Stir phase B into phase Awith homogenization, and briefly afterhomogenize. Slurry phase C, stirinto phase AB, neutralize with phase D and afterhomogenize. Cool toabout 40° C., add phase E, homogenize again.

Application Example 36 Transparent Soap

4.20 sodium hydroxide 3.60 dist. water  2.0 polymer according toPreparation Example 3 22.60  propylene glycol 18.70  glycerol 5.20cocoamide DEA 10.40  cocamine oxide 4.20 sodium lauryl sulfate 7.30myristic acid 16.60  stearic acid 5.20 tocopherol

Preparation:

Mix all ingredients. Melt the mixture at 85° C. until clear. Immediatelypour into the mold.

Application Example 37 Peeling Cream, O/W Type

Phase A 3.00 ceteareth-6 1.50 ceteareth-25 3.00 glyceryl stearate 5.00cetearyl alcohol, sodium cetearyl sulfate 6.00 cetearyl octanoate 6.00mineral oil 0.20 bisabolol Phase B 2.00 propylene glycol 0.10 disodiumEDTA 3.00 polymer according to Preparation Example 3 q.s. preservative59.70  dist. water Phase C 0.50 tocopheryl acetate q.s. perfume oilPhase D 10.00  polyethylene

Preparation:

Heat phases A and B separately to about 80° C. Stir phase B into phase Aand homogenize. Cool to about 40° C., add phase C and briefly homogenizeagain. Then stir in phase D.

Application Example 38 Shaving Foam

6.00 ceteareth-25 5.00 poloxamer 407 52.00  dist. water 1.00triethanolamine 5.00 propylene glycol 1.00 PEG-75 lanolin oil 5.00polymer according to Preparation Example 3 q.s. preservative q.s.perfume oil 25.00  sodium laureth sulfate

Preparation:

Weigh everything together, then stir until dissolved. Containerizing: 90parts of active substance and 10 parts of 25:75 propane/butane mixture.

Application Example 39 Aftershave balm

Phase A 0.25 acrylates/C10-30 alkyl acrylate crosspolymer 1.50tocopheryl acetate 0.20 bisabolol 10.00  caprylic/capric triglycerideq.s. perfume oil 1.00 PEG-40 hydrogenated castor oil Phase B 1.00panthenol 15.00  alcohol 5.00 glycerol 0.05 hydroxyethylcellulose 1.92polymer according to Preparation Example 3 64.00  dist. water Phase C0.08 sodium hydroxide

Preparation:

Mix the components of phase A. Stir phase B into phase A withhomogenization, then briefly afterhomogenize. Neutralize with phase Cand homogenize again.

Application Example 40 Bodycare Cream

Phase A 2.00 ceteareth-6 2.00 ceteareth-25 2.00 cetearyl alcohol 3.00glyceryl stearate SE 5.00 mineral oil 4.00 jojoba (Buxus chinensis) oil3.00 cetearyl octanoate 1.00 dimethicone 3.00 mineral oil, lanolinalcohol Phase B 5.00 propylene glycol 0.50 veegum 1.00 panthenol 1.70polymer according to Preparation Example 4 6.00 polyquaternium-44 q.s.preservative 60.80  dist. water Phase C q.s. perfume oil

Preparation:

Heat phases A and B separately to about 80° C. Homogenize phase B. Stirphase B into phase A with homogenization, then briefly afterhomogenize.Cool to about 40° C., add phase C and briefly homogenize again.

Application Example 41 Toothpaste

Phase A 34.79  dist. water 3.00 polymer according to Preparation Example3 0.30 preservative 20.00  glycerol 0.76 sodium monofluorophosphatePhase B 1.20 sodium carboxymethylcellulose Phase C 0.80 aroma oil 0.06saccharin 0.10 preservative 0.05 bisabolol 1.00 panthenol 0.50tocopheryl acetate 2.80 silica 1.00 sodium lauryl sulfate 7.90 dicalciumphosphate anhydrate 25.29  dicalcium phosphate dihydrate 0.45 titaniumdioxide

Preparation:

Dissolve phase A. Spread phase B into phase A and dissolve. Add phase Cand stir under reduced pressure at RT for about 45 min.

Application Example 42 Mouthwash

Phase A 2.00 aroma oil 4.00 PEG-40 hydrogenated castor oil 1.00bisabolol 30.00  alcohol Phase B 0.20 saccharin 5.00 glycerol q.s.preservative 5.00 poloxamer 407 0.5  polymer according to PreparationExample 3 52.30  dist. water

Preparation:

Dissolve phase A and phase B separately until clear. Stir phase B intophase A.

Application Example 43 Denture Adhesive

Phase A 0.20 bisabolol 1.00 beta-carotene q.s. aroma oil 20.00  cetearyloctanoate 5.00 silica 33.80  mineral oil Phase B 5.00 polymer accordingto Preparation Example 3 35.00  PVP (20% strength solution in water)

Preparation:

Thoroughly mix phase A. Stir phase B into phase A.

Application Example 32 Skincare Cream, O/W Type

Phase A 8.00 cetearyl alcohol 2.00 ceteareth-6 2.00 ceteareth-25 10.00 mineral oil 5.00 cetearyl octanoate 5.00 dimethicone Phase B 3.00polymer according to Preparation Example 3 2.00 panthenol, propyleneglycol q.s. preservative 63.00  dist. water Phase C q.s. perfume oil

Preparation:

Heat phase A and B separately to about 80° C. Stir phase B into phase Awith homogenization, then briefly afterhomogenize. Cool to about 40° C.,add phase C, homogenize again.

Application Example 44 Skincare Cream, W/O Type

Phase A 6.00 PEG-7 hydrogenated castor oil 8.00 cetearyl octanoate 5.00isopropyl myristate 15.00  mineral oil 2.00 PEG-45/dodecyl glycolcopolymer 0.50 magnesium stearate 0.50 aluminum stearate Phase B 3.00glycerol 3.30 polymer according to Preparation Example 3 0.70 magnesiumsulfate 2.00 panthenol q.s. preservative 48.00  dist. water Phase C 1.00tocopherol 5.00 tocopheryl acetate q.s. perfume oil

Preparation:

Heat phases A and B separately to about 80° C. Stir phase B into phase Aand homogenize. Cool to about 40° C., add Phase C and briefly homogenizeagain.

Application Example 45 Lipcare Cream

Phase A 10.00  cetearyl octanoate 5.00 polybutene Phase B 0.10 carbomerPhase C 2.00 ceteareth-6 2.00 ceteareth-25 2.00 glyceryl stearate 2.00cetyl alcohol 1.00 dimethicone 1.00 benzophenone-3 0.20 bisabolol 6.00mineral oil Phase D 8.00 polymer according to Preparation Example 3 3.00panthenol 3.00 propylene glycol q.s. preservative 54.00  dist. waterPhase E 0.10 triethanolamine Phase F 0.50 tocopheryl acetate 0.10tocopherol q.s. perfume oil

Preparation:

Dissolve phase A until clear. Add phase B and homogenize. Add phase Cand melt at 80° C. Heat phase D to 80° C. Add phase D to phase ABC andhomogenize. Cool to about 40° C., add phase E and phase F, homogenizeagain.

Application Example 46 Glossy Lipstick

Phase A 5.30 candelilla (Euphorbia cerifera) wax 1.10 beeswax 1.10microcrystalline wax 2.00 cetyl palmitate 3.30 mineral oil 2.40 castoroil, glyceryl ricinoleate, octyldodecanol, carnauba, candelilla wax,0.40 bisabolol 16.00  cetearyl octanoate 2.00 hydrogenatedcocoglycerides q.s. preservative 1.00 polymer according to PreparationExample 3 60.10  castor (Ricinus communis) oil 0.50 tocopheryl acetatePhase B: 0.80 C.I. 14 720:1, Acid Red 14 Aluminum Lake Phase C: 4.00mica, titanium dioxide

Preparation:

Weigh in the components of phase A and melt. Incorporate phase B untilhomogeneous. Add phase C and stir in. Cool to room temperature withstirring.

Example 47 Clear Conditioning Shampoo

A 15.00  cocamidopropylbetaine 10.00  disodium cocoamphodiacetate 5.00polysorbate 20 5.00 decyl glucoside q.s. perfume q.s. preservative0.1-1.0 graft polymer according to Example 3 2.00 laureth-3 ad 100 aqua,demin. q.s. citric acid B: 3.00 PEG-150 distearate

Preparation:

Weigh in the components of Phase A and dissolve. Adjust the pH to 6-7.Add phase B and heat to 50° C. Allow to cool to room temperature withstirring.

Example 48 Shampoo

30.00  sodium laureth sulfate 6.00 sodium cocoamphoacetate 6.00cocamidopropylbetaine 3.00 sodium laureth sulfate, glycol distearate,cocamide MEA, laureth-10 0.1-1.0 graft polymer according to Example 32.00 dimethicone q.s. perfume/q.s. preservative/q.s. citric acid 1.00sodium chloride ad 100 aqua, demin.

Preparation of Examples 48 to 55:

Weigh in the components and dissolve. Adjust the pH to 6-7.

Example 49 Shampoo

30.00  sodium laureth sulfate 6.00 sodium cocoamphoacetate 6.00cocamidopropylbetaine 3.00 sodium laureth sulfate, glycol distearate,cocamide MEA, laureth-10 0.1-1.0 graft polymer according to Example 32.00 amodimethicone q.s. perfume/q.s. preservative/q.s. citric acid 1.00sodium chloride ad 100 aqua, demin.

Example 50 Shampoo

40.00  sodium laureth sulfate 10.00  cocamidopropylbetaine 3.00 sodiumlaureth sulfate, glycol distearate, cocamide MEA, laureth-10 0.1-1.0graft polymer according to Example 3 2.00 Dow Corning 3052 q.s.perfume/q.s. preservative/q.s. citric acid 2.00 cocamido DEA ad 100aqua, demin.

Example 51 Antidandruff Shampoo

40.00 sodium laureth sulfate 10.00 cocamidopropylbetaine 10.00 disodiumlaureth sulfosuccinate  2.50 sodium laureth sulfate, glycol distearate,cocamide MEA, laureth-10 0.1-1.0 graft polymer according to Example 3 0.50 climbazole q.s. perfume/q.s. preservative/0.50 sodium chloride ad100 aqua, demin.

Example 52 Shampoo

25.00  sodium laureth sulfate 5.00 cocamidopropylbetaine 2.50 sodiumlaureth sulfate, glycol distearate, cocamide MEA, laureth-10 0.1-1.0graft polymer according to Example 3 q.s. perfume q.s. preservative 2.00cocamido DEA ad 100 aqua, demin.

Example 53 Shampoo

20.00  ammonium laureth sulfate 15.00  ammonium lauryl sulfate 5.00cocamidopropylbetaine 2.50 sodium laureth sulfate, glycol distearate,cocamide MEA, laureth-10 0.1-1.0 graft polymer according to Example 3q.s. perfume q.s. preservative 0.50 sodium chloride ad 100 aqua, demin.

Example 54 Clear Shower Gel

40.00  sodium laureth sulfate 5.00 decyl glucoside 5.00cocamidopropylbetaine 0.1-1.0 graft polymer according to Example 31.00 panthenol q.s. perfume/q.s. preservative/q.s. citric acid 2.00 sodiumchloride ad 100 aqua, demin.

Example 55 Shampoo

12.00  sodium laureth sulfate 1.50 decyl glucoside 2.50cocamidopropylbetaine 5.00 cocoglucoside glyceryl oleate 2.00 sodiumlaureth sulfate, glycol distearate, cocamide MEA, laureth-10 0.1-1.0graft polymer according to Example 3 q.s. preservative/q.s. SunsetYellow C.I. 15 985/q.s. perfume 1.00 sodium chloride ad 100 aqua, demin.

Example 56 Shampoo

A 40.00  sodium laureth sulfate 5.00 sodium C12-15 pareth-15 sulfonate5.00 decyl glucoside q.s. perfume 0.10 phytantriol B ad 100 aqua, demin.0.1-1.0 graft polymer according to Example 3 1.00 panthenol q.s.preservative 1.00 laureth-3 q.s. citric acid 2.00 sodium chloride

Preparation:

Weigh in the components of Phase A and dissolve. Adjust pH to 6-7. Addphase B and mix.

1. A graft polymer obtainable by free-radical graft polymerization of a)at least one N-vinyl-containing monomer b) optionally one or morefurther copolymerizable monomers onto a polymeric graft base c), whichcomprises at least one compound from the group c1) and at least onecompound from the group c2), where c1) represents polyether-containingcompounds c2) represents polymers which comprise at least 5% by weightof vinylpyrrolidone units d) optionally at least one crosslinker.
 2. Agraft polymer as claimed in claim 1, wherein the graft polymer iswater-soluble or water-dispersible.
 3. A graft polymer as claimed inclaim 1, wherein N-vinylamides and/or N-vinyllactams are used as monomera).
 4. A graft polymer as claimed in claim 1, wherein at least oneopen-chain N-vinylamide compound of the formula (I)

where R¹, R², R³═H or C₁— to C₆-alkyl, is used as monomer a).
 5. A graftpolymer as claimed in claim 4, where the radicals R¹, R² and R³ informula (I)=H.
 6. A graft polymer as claimed in claim 1, whereinN-vinyllactams of the formula (II)

where n=1, 2, 3, are used as monomer a).
 7. A graft polymer as claimedin claim 1, wherein the polyether-containing compound c1) is chosen frompolymers of the formula III

in which the variables, independently of one another, have the followingmeanings: R¹ is hydrogen, C₁-C₂₄-alkyl, R⁶—C(═O)—, R⁶—NH—C(═O)—,polyalcohol radical; R⁵ is hydrogen, C₁-C₂₄-alkyl, R⁶—C(═O)—,R⁶—NH—C(═O)—; R² to R⁴ are —(CH₂)₂—, —(CH₂)₃—, —(CH₂)₄—, —CH₂—CH(R⁶),—CH₂—CHOR⁷—CH₂—; R⁶ is C₁-C₂₄-alkyl; R⁷ is hydrogen, C₁-C₂₄-alkyl,R⁶—C(═O)—, R⁶—NH—C(═O)—; A is —C(═O)—O, —C(═O)—B—C(═O)—O,—CH₂—CH(—OH)—B—CH(—OH)—CH₂—O, —C(═O)—NH—B—NH—C(═O)—O;

B is —CH₂)_(t)—, arylene, optionally substituted; R³⁰, R³¹ are hydrogen,C₁-C₂₄-alkyl, C₁-C₂₄-hydroxyalkyl, benzyl or phenyl; n is 1 when R¹ isnot a polyalcohol radical or n is 1 to 1000 when R¹ is a polyalcoholradical s=0 to 1000; t=1 to 12; u=1 to 5000;v=0 to 5000; w=0 to 5000;x=0 to 5000; y=0 to 5000; z=0 to
 5000. 8. A graft polymer as claimed inclaim 1, wherein the polyether-containing compound c1) is chosen frompolymers of the formula III in which the variables, independently of oneanother, have the following meanings: R¹ is hydrogen, C₁-C₆-alkyl,R⁶—C(═O)—, R⁶—NH—C(═O)—; R⁵ is hydrogen, C₁-C₆-alkyl, R⁶—C(═O)—,R⁶—NH—C(═O)—; R² to R⁴ are —(CH₂)₂—, —(CH₂)₃—, —(CH₂)₄—, —CH₂—CH(R⁶)—,—CH₂—CHOR⁷—CH₂—; R⁶ is C₁-C₆-alkyl; R⁷ is hydrogen, C₁-C₆-alkyl,R⁶—C(═O)—, R⁶—NH—C(═O)—; n=1; s=0; u=5 to 500; v=0 to 500; w=0 to 500.9. A graft polymer as claimed in claim 1, wherein thepolyether-containing compound c1) is chosen from polymers obtainable byreacting polyethylenimines with alkylene oxides.
 10. A graft polymer asclaimed in claim 1, wherein the polyether-containing compounds c1) havebeen prepared by polymerization of ethylenically unsaturated alkyleneoxide-containing monomers and optionally further copolymerizablemonomers.
 11. A graft polymer as claimed in claim 10, wherein thepolyether-containing compounds c1) have been prepared by polymerizationof polyalkylene oxide vinyl ethers and optionally furthercopolymerizable monomers.
 12. A graft polymer as claimed in claim 10,wherein the polyether-containing compounds c1) have been prepared bypolymerization of polyalkylene oxide(meth)acrylates and optionallyfurther copolymerizable monomers.
 13. A graft polymer as claimed inclaim 1, wherein the further comonomers of N-vinylpyrrolidone for thesynthesis of the graft base c2) are chosen from the group:N-vinylcaprolactam, N-vinylimidazole and alkyl-substitutedN-vinylimidazoles, and salts thereof with carboxylic acids or mineralacids, and quaternized products thereof, unsaturated sulfonic acids,diallyldimethylammonium chloride, vinyl esters, vinyl ethers, styrene,alkylstyrenes, monoethylenically unsaturated carboxylic acids and salts,esters, amides and nitriles thereof, maleic anhydride and itsmonoesters, N,N-dialkylaminoalkyl(meth)acrylates, and salts thereof withcarboxylic acids or mineral acids, and the quaternized products.
 14. Agraft polymer as claimed in claim 1, wherein a polymer with avinylpyrrolidone content of at least 10% by weight, in particular atleast 30% by weight, preferably at least 50% by weight, is used as graftbase c2).
 15. A graft polymer as claimed in claim 1, wherein apolyvinylpyrrolidone homopolymer is used as graft base c2).
 16. A graftpolymer as claimed in claim 1, wherein the graft base c used is amixture comprising c1) polyalkylene glycols and c2) polymers whichcomprise at least 50% by weight of vinylpyrrolidone units.
 17. A graftpolymer as claimed in claim 1, wherein the graft base c used is amixture comprising c1) polyalkylene glycols and c2) polymers whichcomprise at least 50% by weight of vinylpyrrolidone units and thefree-radical graft polymerization is carried out in the presence of acrosslinker d).
 18. A graft polymer as claimed in claim 1, wherein thegraft base c used is a mixture comprising c1) polyalkylene glycols undc2) polyvinylpyrrolidone homopolymers.
 19. A graft polymer as claimed inclaim 1, wherein the graft base c used is a mixture comprising c1)polyalkylene glycols and c2) polyvinylpyrrolidone homopolymers and thefree-radical graft polymerization is carried out in the presence of acrosslinker d).
 20. A graft polymer as claimed in claim 1, wherein thefurther comonomers b) are compounds chosen from the group consisting ofmonoethylenically unsaturated carboxylic acids and the salts, esters,amides and nitriles of monoethylenically unsaturated carboxylic acids,maleic anhydride and its monoesters, diallyldimethylammonium chloride,vinyl esters, styrene, alkylstyrenes, unsaturated sulfonic acids,N-vinyllactams, vinyl ethers, 1-vinylimidazole and alkyl-substitutedvinylimidazoles, and salts thereof with carboxylic acids or mineralacids, and quaternized products thereof, N,N-dialkylaminoalkyl(meth)acrylates, and quaternized products thereof.
 21. A graft polymeras claimed in claim 1, wherein the polymer is at least partiallyhydrolyzed.
 22. A cosmetic preparation comprising the graft polymer asclaimed in claim
 1. 23. The cosmetic preparation of claim 22 wherein thegraft polymer acts as a thickner.
 24. The cosmetic preparation of claim22 wherein the graft polymer is used as a conditioning agent.
 25. Acosmetic preparation comprising a) 0.01-20% by weight of graft polymersas claimed in claim 1 b) 20-99.99% by weight of water and/or alcohol c)0-79.5% by weight of further constituents.